Fluorescent materials and their use

ABSTRACT

A composition comprising (a) an effective amount of a guest chromophore embedded in a matrix of a host chromophore, or (b) a host chromophore and an effective amount of a guest chromophore both embedded in a polymer matrix, wherein the absorption spectrum of the guest chromophore overlaps with the fluorescence emission spectrum of the host chromophore, and wherein the host chromophore is selected from the group consisting of benzo [4,5]imidazo [2,1 -a]isoindol-11-ones.

[0001] The present invention relates to a composition comprising (a) aneffective amount of a guest chromophore embedded in a matrix of a hostchromophore, or (b) a host chromophore and an effective amount of aguest chromophore both embedded in a polymer matrix, wherein theabsorption spectrum of the guest chromophore overlaps with thefluorescence emission spectrum of the host chromophore, and wherein thehost chromophore is selected from the group consisting of benzo[4,5]imidazo [2,1-a]isoindol-11-ones.

[0002] Further, the present invention relates to a process for thepreparation of this composition, a polymerisable composition comprisingthis composition, a composition comprising a carrier material with ahigh relief of a polymerized photoresist material containing thiscomposition, a process for the preparation of fluorescent high reliefimages on a carrier, the use of the compositions as fluorescentmaterials, especially in electroluminescent devices,and novelnon-functionalized benzo[4,5]imidazo[2,1-a] isoindol-11-one derivatives.

[0003] Combinations comprising host chromophores with guest chromophoresdissolved therein to generate materials with enhanced fluorescence andlarge differences between absorption maximum and emission maximum arehighly desired materials that possess a wide range of potential andactual technical applications. The large difference between theabsorption (excitation) maximum and the emission maximum is due to theoccurrence of resonant energy transfer between the respective host andguest chromophores.

[0004] The possibility of energy transfer between chromophores thatpossess an area of overlap of the absorption spectrum of a guestchromophore with the fluorescence emission spectrum of a host is known.For example, H. Port et al. describe in Z. Naturforsch., 36a, pages 697to 704 (1981) mixed crystals of fluorene doped with dibenzofurane orbenzindan with an enhanced fluorescence in the UV region at temperaturesbelow 100 K. However, the low temperature fluorescence has no practicalvalue and is only of scientific interest.

[0005] C. W. Tang et al. disclose in J. Appl. Phys., 65, 3610 to 3616(1989) a multilayered electroluminescent device with a light emittinglayer composed of 8-hydroxyquinoline aluminum, in which is embedded azone doped with a fluorescent molecule such as coumarin. The deviceshows improved electroluminescence and an effective Stoke's color shiftwhich is dependent on the particular dopant. The manufacture of thedevice is complicated and not readily suitable for an industrialproduction.

[0006] J. M. Lang et al. describe in J. Phys. Chem. 97, pages 5058 to5064 (1993) the combination of coumarin as host and rhodamine as guestwhereby both components are dissolved in polyacrylic acid, but Lang'sstudy demonstrates enhanced fluorescence only under high pressure.

[0007] In WO 93/23492 are disclosed fluorescent microparticles with anenhanced Stokes shift, which are composed of soluble and fluorescenthost and guest dyes absorbed or bonded to polymeric microparticles. Thematerial is used for the optical detection of nucleic acids like DNA orRNA. Unfavorably, the solid state fluorescence of these microparticlesis poor.

[0008] U.S. Pat. No. 5,227,252 discloses a fluorescent composition of8-hydroxyquinoline aluminum as host and quinacridones as guest.Similarly, JP-A-05 320 633 discloses a fluorescent composition of8-hydroxyquinoline aluminum as host and diketopyrrolopyrroles as guest.However, in both documents, the guests are insoluble materials, they aredissolved mainly as microsized clusters. The occurrence of microsizedclusters is due to co-sublimation processes being the means ofpreparation. The materials possess a larger Stoke's shifts than would beanticipated by normal single component fluorescent materials, and areused for example as light emitting materials in electroluminescentdevices. The process for their manufacture requires large expenditureson technical equipment to ensure the careful control process conditionssuch as vacuum and temperature, to achieve the desired mixed material.The process is not convenient for large scale industrial manufacture.

[0009] In EP-A-0 456 609 is disclosed a process for the preparation of1,2,3,4-tetrachloro-benzo[4,5]imidazo[2,1-a]isoindol-11-one and itsderivatives in the presence of selected solvents. These compounds arepigments showing solid state fluorescence and improved outdoordurability. It is also mentioned therein, that the combination of 95% ofthe yellow 1,2,3,4-tetrachlorobenzo[4,5]imidazo[2,1-a]isoindol-11-onewith 5% of Indanthrone Blue generates a green fluorescent pigment.Hence, such a system is a pigment composite, wherein the new colorgenerated is simply a sum of the two component colors. The color is notcreated by virtue of the occurrence of complex, molecular level, energytransfer processes that require close interaction between the componentsof the mixture.

[0010] F. W. Harris et.al. describe in ACS Symp. Ser. 132, 39 (1980) thecompound 1,2,3,4-tetraphenyl-benzo [4,5] imidazo [2,1-a] isoindol-11-oneas a model material, as a part of their investigations into phenylatedpolyimidazopyrrolones for potential use in aerospace applications.However, no reference to its fluorescence behavior is made.

[0011] Hence, the object of the invention on hand was to find afluorescent composition, which does not show the above mentioneddisadvantages, preferably a composition should be provided which

[0012] has a greatly enhanced and intense fluorescence emission,

[0013] shows an intense solid state fluorescence, wherein the emissionspectrum is preferably in the visible region of the electromagneticspectrum,

[0014] is excitable using wavelengths in both the UV and visibleregions,

[0015] shows a very excellent photostability and outdoor durability,

[0016] shows a wide range of emission spectra through selection ofsuited guest molecules (color tuning),

[0017] has a high thermal stability,

[0018] is easily prepared, i.e. by a (co-)precipitation process,

[0019] can be used for the preparation of electroluminescence devices,if the host chromophore is selected from the group consisting ofbenzo[4,5]imidazo[2,1-a]isoindol-11-ones, which means derivatives ofbenzo[4,5]imidazo[2,1-a]isoindol-11-one as the fundamental substance.

[0020] In addition, the enhancement factor for the present compositionspreferably should be all positive and should be at least 1.3, morepreferably at least 2 and most preferably at least 5. The term“enhancement factor” as used herein, is defined as the increased ordecreased factor, in terms of peak height emission intensities of asolid-state powder comprising of host and guest fluorescent moietiescompared to an identical powder that does not contain any fluorescentguest moieties. Comparisons are considered real, for as long as theexcitation radiation wavelengths are identical. In general, the emissionwavelengths of host/guest material occur at longer wavelengths (lowerenergy) as compared to an identical material with no guest component.

[0021] Accordingly, a composition was found comprising (a) an effectiveamount of a guest chromophore embedded in a matrix of a hostchromophore, or (b) a host chromophore and an effective amount of aguest chromophore both embedded in a polymer matrix, wherein theabsorption spectrum of the guest chromophore overlaps with thefluorescence emission spectrum of the host chromophore, and wherein thehost chromophore is selected from the group consisting of benzo[4,5]imidazo [2,1-a] isoindol-11-ones.

[0022] In addition, a process for the preparation of this composition, apolymerizable composition comprising this composition, a compositioncomprising a carrier material with a high relief of a polymerizedphotoresist material containing this composition, a process for thepreparation of fluorescent high relief images on a carrier, the use ofthe compositions as fluorescent materials, esp. in electroluminescentdevices, and novel non-functionalizedbenzo[4,5]imidazo[2,1-a]isoindol-11-one derivatives were found, too.

[0023] A first embodiment of the present invention relates to acomposition comprising (a) an effective amount of a guest chromophoreembedded in a matrix of a host chromophore, or (b) a host chromophoreand an effective amount of a guest chromophore both embedded in apolymer matrix, wherein the absorption spectrum of the guest chromophoreoverlaps with the fluorescence emission spectrum of the hostchromophore, and wherein the host chromophore is selected from the groupconsisting of benzo [4,5] imidazo [2,1-a] isoindol-11-ones.

[0024] The host chromophore is selected from the group consisting ofderivatives of benzo[4,5]imidazo[2,1-a]isoindol-11-one andbenzo[4,5]imidazo[2,1-a]isoindol-11-one (hereinafter referred to asbenzoimidazoisoindolone(s)) itself. The compounds are preferablyderivatives that are soluble in an organic or aqueous solvent.

[0025] Under the aspects of the invention solubility of hostchromophores means preferably that at least 10 mg, more preferably atleast 50 mg and most preferably at least 100 mg of thebenzoimidazoisoindolone derivative are soluble in 1 liter of solventlike dimethylformamide, at 20° C. It is self-evident, that thesolubilities are higher at increasing temperatures and depend on thechoice of a solvent.

[0026] The benzoimidazoisoindolones may correspond to the formula I

[0027] wherein the neighboring carbon atoms of the benzene rings 1 and 2are uncondensed or condensed with benzene rings, heteroaromatic rings,aliphatic rings, or heteroaliphatic rings, and wherein the benzene rings1 or 2 or both, the condensed ring moieties or all are unsubstituted orsubstituted with organic groups and/or halogen atoms.

[0028] The groups forming a condensed ring are preferably selected fromthe group consisting of bivalent residues of formulae —CH═CH—CH═CH—,—CH═CH—N═CH—, —CH═CH—CH═N—, —CH═N—CH═N—, —CH═CH—NR₁—, —CH═N—CH₂—,—CH═CH—S—, —CH═CH—O—, —(CH₂)₃—, —(CH₂)₄—, —CH₂—CH₂—NR₁—CH₂—,—CH₂—CH₂—CH₂—NR₁—, —CH₂—CH₂—O—CH₂—, —CH₂—CH₂—CH₂—O—, —CH₂—CH₂—S—CH₂—,—CH₂—CH₂—CH₂S—, —CH₂—O—CH₂—, —CH₂—CH₂—O—, —CH₂—S—CH₂—, and —CH₂—CH₂—S—,wherein R₁ is H or an organic substituent, and the bivalent residues areunsubstituted or substituted with an organic group.

[0029] R₁, as organic substituent, may be linear or branched C₁ toC₂₀alkyl, C₅ to C₇cycloalkyl, benzyl or R₂—C(O)—, wherein R₂ is C₁ toC₂₀alkyl, which is unsubstituted or substituted with F, Cl or C₁ toC₁₂alkoxy, or C₅ to C₇cycloalkyl, phenyl or benzyl, which are isunsubstituted or substituted with F, Cl, C₁ to C₁₂alkyl, or C₁ toC₁₂alkoxy.

[0030] Preferred examples for R₁ are H, methyl, ethyl, propyl, butyl,pentyl, hexyl, benzyl, methylbenzyl, dimethylbenzyl, acetyl, propionyl,butyroyl, benzyl-C(O)—, phenyl-C(O)—, toluyl-C(O)—, mono-, di- ortri-chloroacetyl, and mono-, di- or tri-fluoroacetyl, mono- anddichlorophenyl-C(O)—.

[0031] The organic substituent may be selected from the group consistingof halogen, —CN, —NO₂, C₁ to C₁₈ alkyl, C₂ to C₁₈alkenyl, C₂ toC₁₈alkinyl, C₁ to C₁₈ hydroxyalkyl, C₁ to C₁₈ halogenalkyl, C₃ to C₁₂cycloalkyl, C₆ to C₁₈ aryl, C₅ to C₁₇ heteroaryl, C₃ to C₁₂cycloalkylalkyl, C₆ to C₁₈ aralkyl, C₅ to C₁₇ heteroaralkyl, C₁ to C₁₈alkyloxy, C₃ to C₁₂ cycloalkyloxy C₆ to C₁₈ aryloxy, C₅ to C₁₇heteroaryloxy, C₃ to C₁₂ cycloalkylalkyloxy, C₆ to C₁₈ aralkyloxy, C₅ toC₁₇ heteroaralkyloxy, C₁ to C₁₈ alkylthio, C₃ to C₁₂ cycloalkylthio, C₆to C₁₈ arylthio, C₅ to C₁₇ heteroarylthio, C₃ to C₁₂cycloalkylalkylthio, C₆ to C₁₈ aralkylthio, C₅ to C₁₇ heteroaralkylthio,C₁ to C₁₈ alkyl-SO— or —SO₂, C₃ to C₁₂ cycloalkyl-SO— or —SO₂, C₆ toC₁₈aryl-SO— or —SO₂, C₅ to C₁₇ heteroaryl-SO— or —SO₂, C₃ to C₁₂cycloalkylalkyl-SO— or —SO₂, C₆ to C₁₈ aralkyl-SO— or —SO₂, C₁ to C₁₈alkyl-CO—, C₃ to C₁₂ cycloalkyl-CO—, C₆ to C₁₈aryl-CO—, C₅ to C₁₇heteroaryl-CO—, C₃ to C₁₂ cycloalkylalkyl-CO—, C₆ to C₁₈ aralkyl-CO—, C₅to C₁₇ heteroaralkyl-CO—, —NR₃R₄, alkoxyalkyl with 2 to 20 carbon atoms,polyoxyalkylene-OR₆, —X—(R₅)_(k)—C(O)—NR₃R₄, —X—(R₅)_(k)—C(O)—OR₆,—X—(R₅)_(k)—SO₂—OR₆, —X—(R₅)_(k) —SO₂—NR₃R₄, —NH—C(O)—R₆ and —O—C(O)—R₆,wherein

[0032] R₃ and R₄ independently from one another mean H, C₁ to C₂₀alkyl,cyclopentyl, cyclohexyl, phenyl, benzyl, C₁ to C₁₂alkylphenyl or C₁ toC₁₂alkylbenzyl, or R₃ and R₄ together mean tetramethylene,pentamethylene, or the groups —CH₂—CH₂—O—CH₂—CH₂— or—CH₂—CH₂—NR₃—CH₂—CH₂—,

[0033] R₅ is C₁ to C₁₂alkylene, phenylene or benzylene,

[0034] R₆ means H, C₁ to C₂₀alkyl, cyclopentyl, cyclohexyl, phenyl,benzyl, C₁ to C₁₂alkylphenyl or C₁ to C₁₂alkylbenzyl,

[0035] X is a direct bond, —O— or S,

[0036] k is 0 or 1 and

[0037] and the salts of the acids.

[0038] Preferred salts are the alkaline metal and earth alkaline metalsalts, e.g. from Li, Na, K, Mg, Ca, Sr, Ba.

[0039] The cyclic aliphatic and aromatic residues (substituents for theorganic group) may be also substituted, for example with halogen like F,Cl or Br, —CN, —NO₂, C₁ to C₁₈alkyl, C₃ to C₁₂ cycloalkyl, C₆ to C₁₈aryl, C₃ to C₁₂ cycloalkylalkyl, C₆ to C₁₈ aralkyl, C₅ to C₁₇heteroaralkyl C₁ to C₁₈ alkyloxy, C₃ to C₁₂ cycloalkyloxy, C₆ to C₁₈aryloxy.

[0040] In the context of the invention the alkyl substituent may belinear or branched and contains preferably 1 to 12 C-atoms, morepreferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms andparticularly preferred 1 to 4 C-atoms. Some examples are methyl, ethyl,n- or i-propyl, n-, i- or t-butyl, and the isomers of pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl and octadecyl.

[0041] In the context of the invention the halogen substituent may be F,Cl, Br or I and is preferably F or Cl.

[0042] In the context of the invention the alkenyl substituent may belinear or branched and contains preferably 2 to 12 C-atoms, morepreferably 2 to 8 C-atoms, most preferably 2 to 6 C-atoms andparticularly preferred 2 to 4 C-atoms. Some examples are vinyl, allyl,methylvinyl, but-1-ene-4-yl, but-2-ene-4-yl, but-3-ene-4-yl,3-methyl-prop-1-ene-3-yl, and the isomers of pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undeencyl, dodecenyl, tridecenyl,tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl.

[0043] In the context of the invention the alkinyl substituent may belinear or branched and contains preferably 2 to 12 C-atoms, morepreferably 2 to 8 C-atoms, most preferably 2 to 6 C-atoms andparticularly preferred 2 to 4 C-atoms. Some examples are ethinyl,crotonyl, methylethinyl, but-1-ine-4-yl, but-2-ine-4-yl, but-3-ine-4-yl,3-methyl-prop-1-in-3-yl, and the isomers of pentinyl, hexinyl, heptinyl,octinyl, noninyl, decinyl, undecinyl, dodecinyl, tridecinyl,tetradecinyl, pentadecinyl, hexadecinyl, heptadecinyl and octadecinyl.

[0044] In the context of the invention the hydroxyalkyl substituent maybe linear or branched and contains preferably 1 to 12 C-atoms, morepreferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms andparticularly preferred 1 to 4 C-atoms. Some examples are hydroxymethyl,hydroxyethyl, n- or i-hydroxypropyl, n-, i- or t-hydroxybutyl, and theisomers of hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl,hydroxynonyl, hydroxydecyl, hydroxyundecyl, hydroxydodecyl,hydroxytridecyl, hydroxytetradecyl, hydroxypentadecyl, hydroxyhexadecyl,hydroxyheptadecyl and hydroxyoctadecyl.

[0045] In the context of the invention the halogenalkyl substituent maybe linear or branched and contains preferably 1 to 12 C-atoms, morepreferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms andparticularly preferred 1 to 4 C-atoms. The halogen may be F, Cl, Br orI, and is preferably F and Cl. Some examples are chloromethyl,dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,trifluoromethyl, chloroethyl, n- or i-chloropropyl, n-, i- ort-chlorobutyl, perfluoroethyl and perfluorobutyl.

[0046] In the context of the invention the cycloalkyl substituentcontains preferably 4 to 8 and more preferred 5 to 7 ring carbon atoms.Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl and cyclododecyl. Preferred groups arecyclopentyl and cyclohexyl.

[0047] In the context of the invention the aryl substituent may benaphthyl or preferably phenyl.

[0048] In the context of the invention the heteroaryl substituentcontains preferably 5 or 6 ring atoms and preferably 1 to 3, morepreferably 1 or 2 heteroatoms selected from the group consisting of O, Sand N. Some examples are pyridinyl, pyrimidinyl, furanyl, pyrrolyl andthiophenyl.

[0049] In the context of the invention the cycloalkyl-alkyl substituentis preferably cycloalkyl-methyl or -ethyl, and cycloalkyl meanspreferably cyclopentyl or cyclohexyl.

[0050] In the context of the invention the aralkyl substituent ispreferably arylmethyl or -ethyl, and aryl means preferably phenyl ornaphthyl. Some examples are benzyl, phenylethyl and naphthylmethyl.

[0051] In the context of the invention the heteroaralkyl substituent ispreferably heteroarylmethyl or -ethyl, and the heteroaryl containspreferably 5 or 6 ring atoms and preferably 1 to 3, more preferably 1 or2 heteroatoms selected from group consisting of O, S and N. Someexamples are pyridinylmethyl or -ethyl, pyrimidinyl, furanylmethyl,pyrrolylmethyl and thiophenylmethyl.

[0052] In the context of the invention the alkoxy substituent may belinear or branched and contains preferably 1 to 12 C-atoms, morepreferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms andparticularly preferred 1 to 4 C-atoms. Some examples are methoxy,ethoxy, n- or i-propoxy, n-, i- or t-butoxy, and the isomers of pentoxy,hexoxy, heptoxy, octoxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy,tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxyand octadecyloxy.

[0053] In the context of the invention the cycloalkyloxy substituentcontains preferably 4 to 8 and more preferred 5 to 7 ring carbon atoms.Examples are cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,cyclohexyloxy, cycloheptyloxy, cyclooctyloxy and cyclododecyloxy.Preferred groups are cyclopentyloxy and cyclohexyloxy.

[0054] In the context of the invention the aryloxy substituent may benaphthyloxy or preferably phenyloxy.

[0055] In the context of the invention the heteroaryloxy substituentcontains preferably 5 or 6 ring atoms and preferably 1 to 3, morepreferably 1 or 2 heteroatoms selected from group consisting of O, S andN. Some examples are pyridinyloxy, pyrimidinyloxy, furanyloxy,pyrrolyloxy and thiophenyloxy.

[0056] In the context of the invention the cycloalkyl-alkyloxysubstituent is preferably cycloalkyl-methyloxy or -ethyloxy, andcycloalkyl means preferably cyclopentyl or cyclohexyl.

[0057] In the context of the invention the aralkyloxy substituent ispreferably arylmethyloxy or -ethyloxy, and aryl means preferably phenylor naphthyl. Some examples are benzyloxy, phenylethyloxy andnaphthylmethyloxy.

[0058] In the context of the invention the heteroaralkyloxy substituentis preferably heteroarylmethyl or -ethyl, and the heteroaryl containspreferably 5 or 6 ring atoms and preferably 1 to 3, more preferably 1 or2 heteroatoms selected from the group consisting of O, S and N. Someexamples are pyridinylmethyloxy or -ethyloxy, pyrimidinyloxy,furanylmethyloxy, pyrrolylmethyloxy and thiophenylmethyloxy.

[0059] In the context of the invention the alkylthio substituent may belinear or branched and contains preferably 1 to 12 C-atoms, morepreferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms andparticularly preferred 1 to 4 C-atoms. Some examples are methylthio,ethylthio, n- or i-propylthio, n-, i- or t-butylthio, and the isomers ofpentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio,undecylthio, dodecylthio, tridecylthio, tetradecylthio, pentadecylthio,hexadecylthio, heptadecylthio and octadecylthio.

[0060] In the context of the invention the cycloalkylthio substituentcontains preferably 4 to 8 and more preferred 5 to 7 ring carbon atoms.Examples are cyclopropylthio, cyclobutylthio, cyclopentylthio,cyclohexylthio, cycloheptylthio, cyclooctylthio and cyclododecylthio.Preferred groups are cyclopentylthio and cyclohexylthio.

[0061] In the context of the invention the arylthio substituent may benaphthylthio or preferably phenylthio.

[0062] In the context of the invention the heteroarylthio substituentcontains preferably 5 or 6 ring atoms and preferably 1 to 3, morepreferably 1 or 2 heteroatoms selected from the group consisting of O,S, N. Some examples are pyridinylthio, pyrimidinylthio, furanylthio,pyrrolylthio and thiophenylthio.

[0063] In the context of the invention the cycloalkyl-alkylthiosubstituent is preferably cycloalkyl-methylthio or -ethylthio, andcycloalkyl means preferably cyclopentyl or cyclohexyl.

[0064] In the context of the invention the aralkylthio substituent ispreferably arylmethylthio or -ethylthio, and aryl means preferablyphenyl or naphthyl. Some examples are benzylthio, phenylethylthio andnaphthylmethylthio.

[0065] In the context of the invention the heteroaralkylthio substituentis preferably heteroarylmethylthio or -ethylthio, and the heteroarylcontains preferably 5 or 6 ring atoms and preferably 1 to 3, morepreferably 1 or 2 heteroatoms selected from group consisting of O, S andN. Some examples are pyridinylmethylthio or -ethylthio, pyrimidinylthio,furanylmethylthio, pyrrolylmethylthio and thiophenylmethylthio.

[0066] In the context of the invention the alkyl-SO— or —SO₂—substituent may be linear or branched and contains preferably 1 to 12C-atoms, more preferably 1 to 8 C-atoms, most preferably 1 to 6 C-atomsand particularly preferred 1 to 4 C-atoms. Some examples are methyl-SO—or —SO₂—, ethyl-SO— or —SO₂—, n- or i-propyl-SO— or —SO₂—, n-, i- ort-butyl-SO— or —SO₂—, and the isomers of pentyl-SO— or —SO₂—, hexyl-SO—or —SO₂—, heptyl-SO— or —SO₂—, octyl-SO— or —SO₂—, nonyl-SO— or —SO₂—,decyl-SO— or —SO₂—, undecyl-SO— or —SO₂—, dodecyl-SO— or —SO₂—,tridecyl-SO— or —SO₂—, tetradecyl-SO— or —SO₂—, pentadecyl-SO— or —SO₂—,hexadecyl-SO— or —SO₂—, heptadecyl-SO— or —SO₂— and octadecyl-SO— or—SO₂—.

[0067] In the context of the invention the cycloalkyl-SO— or —SO₂—substituent contains preferably 4 to 8 and more preferred 5 to 7 ringcarbon atoms. Examples are cyclopropyl-SO— or —SO₂—, cyclobutyl-SO— or—SO₂—, cyclopentyl-SO— or —SO₂—, cyclohexyl-SO— or —SO₂— cycloheptyl-SO—or —SO₂—, cyclooctyl-SO— or —SO₂— and cyclododecyl-SO— or —SO₂—.Preferred groups are cyclopentyl-SO— or —SO₂— and cyclohexyl-SO— orSO₂—.

[0068] In the context of the invention the aryl-SO— or —SO₂— substituentmay be naphthyl-SO— or —SO₂— or preferably phenyl-SO— or —SO₂—.

[0069] In the context of the invention the heteroaryl-SO— or —SO₂—substituent contains preferably 5 or 6 ring atoms and preferably 1 to 3,more preferably 1 or 2 heteroatoms selected from the group consisting ofO, S and N. Some examples are pyridinyl-SO— or —SO₂—, pyrimidinyl-SO— or—SO₂—, furanyl-SO— or —SO₂—, pyrrolyl-SO— or —SO₂— and thiophenyl-SO— or—SO₂—.

[0070] In the context of the invention the cycloalkyl-alkyl-SO— or —SO₂—substituent is preferably cycloalkyl-methyl-SO— or —SO₂— or -ethyl-SO—or —SO₂—, and cycloalkyl means preferably cyclopentyl or cyclohexyl.

[0071] In the context of the invention the aralkyl-SO— or —SO₂—substituent is preferably arylmethyl-SO— or —SO₂— or -ethyl-SO— or—SO₂—, and aryl means preferably phenyl-SO— or —SO₂— or naphthyl-SO— or—SO₂—. Some examples are benzyl-SO— or —SO₂—, phenylethyl-SO— or —SO₂—and naphthylmethyl-SO— or —SO₂—.

[0072] In the context of the invention the heteroaralkyl-SO— or —SO₂—substituent is preferably heteroarylmethyl-SO— or —SO₂— or -ethyl-SO— or—SO₂—, and the heteroaryl contains preferably 5 or 6 ring atoms andpreferably 1 to 3, more preferably 1 or 2 heteroatoms selected from thegroup consisting of O, S and N. Some examples are pyridinylmethyl-SO— or—SO₂— or -ethyl-SO— or —SO₂—, pyrimidinyl-SO— or —SO₂—,furanylmethyl-SO— or —SO₂—, pyrrolylmethyl-SO— or —SO₂— andthiophenylmethyl-SO— or —SO₂—.

[0073] In the context of the invention the alkyl-CO— substituent may belinear or branched and contains preferably 1 to 12 C-atoms, morepreferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms andparticularly preferred 1 to 4 C-atoms. Some examples are methyl-CO—,ethyl-CO—, n- or i-propyl-CO—, n-, i- or t-butyl-CO—, and the isomers ofpentyl-CO—, hexyl-CO—, heptyl-CO—, octyl-CO—, nonyl-CO—, decyl-CO—,undecyl-CO—, dodecyl-CO—, tridecyl-CO—, tetradecyl-CO—, pentadecyl-CO—,hexadecyl-CO—, heptadecyl-CO— and octadecyl-CO—.

[0074] In the context of the invention the cycloalkyl-CO— substituentcontains preferably 4 to 8 and more preferred 5 to 7 ring carbon atoms.Examples are cyclopropyl-CO—, cyclobutyl-CO—, cyclopentyl-CO—,cyclohexyl-CO—, cycloheptyl-CO—, cyclooctyl-CO— and cyclododecyl-CO—.Preferred groups are cyclopentyl-CO— and cyclohexyl-CO—.

[0075] In the context of the invention the aryl-CO— substituent may benaphthyl-CO— or preferably phenyl-CO—.

[0076] In the context of the invention the heteroaryl substituentcontains preferably 5 or 6 ring atoms and preferably 1 to 3, morepreferably 1 or 2 heteroatoms selected from group consisting of O, S andN. Some examples are pyridinyl, pyrimidinyl, furanyl, pyrrolyl andthiophenyl.

[0077] In the context of the invention the cycloalkyl-alkyl-CO—substituent is preferably cycloalkylmethyl-CO— or -ethyl-CO—, andcycloalkyl means preferably cyclopentyl or cyclohexyl.

[0078] In the context of the invention the aralkyl-CO— substituent ispreferably arylmethyl-CO— or -ethyl-CO—, and aryl means preferablyphenyl-CO— or naphthyl-CO—. Some examples are benzyl-CO—,phenylethyl-CO— and naphthylmethyl-CO—.

[0079] In the context of the invention the heteroaralkyl-CO— substituentis preferably hetero-arylmethyl-CO— or -ethyl-CO—, and the heteroarylcontains preferably 5 or 6 ring atoms and preferably 1 to 3, morepreferably 1 or 2 heteroatoms selected from group consisting of O, S andN. Some examples are pyridinylmethyl-CO— or -ethyl-CO—, pyrimidinyl-CO—,furanylmethyl-CO—, pyrrolylmethyl-CO— and thiophenylmethyl-CO—.

[0080] In the context of the invention the alkoxyalkyl substituentcontains preferably in total 2 to 12, more preferably 2 to 8 and mostpreferably 2 to 6 carbon atoms. The alkoxy may contain 1 to 4 carbonatoms. Some examples are methoxyethyl, methoxyethyl, methoxypropyl,methoxybutyl, methoxypentyl, methoxyhexyl, ethoxymethyl, ethoxyethyl,ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, propoxymethyl andbutoxymethyl.

[0081] In the context of the invention the polyoxyalkylene-O—R₆substituent preferably contains 2 to 12 and more preferably 2 to 6oxyalkylene units, wherein alkylene is preferably ethylene, 1,2- or1,3-propylene or 1,2—, 1,3— or 1,4-butylene. R₆ is preferably H or C₁ toC₄alkyl.

[0082] In the context of the invention R₃ and R₄ in the meaning of alkylmay be linear or branched and contain preferably 1 to 12 C-atoms, morepreferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms andparticularly preferred 1 to 4 C-atoms. Some examples are methyl, ethyl,n- or i-propyl, n-, i- or t-butyl, and the isomers of pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl and octadecyl.

[0083] In the context of the invention R₃ and R₄ in the meaning ofalkylphenyl may be preferably C₁ to C₈alkylphenyl, C₁ to C₄alkylphenyl.Some examples are methylbenzyl, ethylphenyl, n- or i-propylphenyl, n-,i- or t-butylphenyl, hexylphenyl, octylphenyl, dodecylphenyl, anddimethylphenyl.

[0084] In the context of the invention R₃ and R₄ in the meaning ofalkylbenzyl may be preferably C₁ to C₈alkylbenzyl, C₁ to C₄alkylbenzyl.Some examples are methylbenzyl, ethylbenzyl, n- or i-propylbenzyl, n-,i- or t-butylbenzyl, hexylbenzyl, octylbenzyl, dodecylbenzyl, anddimethyl benzyl.

[0085] In the context of the invention R₃ and R₄ mean independently fromone another preferably H, C₁ to C₄alkyl, cyclohexyl, phenyl, benzyl, C₁to C₄alkylphenyl or C₁ to C₄alkylbenzyl, or R₃ and R₄ together meantetramethylene, pentamethylene, or the group —CH₂—CH₂—O—CH₂—CH₂—.

[0086] In the context of the invention R₅ in the meaning of alkylene ispreferably C₁ to C₆alkylene, C₁ to C₄alkylene, for example methylene,ethylene, propylene or butylene. Most preferred R₅ is methylene,ethylene, phenylene or benzylene.

[0087] In the context of the invention wherein R₆ is alkyl, it may belinear or branched and contain preferably 1 to 12 C-atoms, morepreferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms andparticularly preferred 1 to 4 C-atoms. Some examples are methyl, ethyl,n- or i-propyl, n-, i- or t-butyl, and the isomers of pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl and octadecyl. R₆ is preferably H, C₁to C₁₂alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl.

[0088] Examples for substituents are F, Cl, Br, methyl, ethyl, propyl,butyl, hexyl, methyloxy, ethyloxy, propyloxy, butyloxy, hexyloxy,methylthio, ethylthio, methyl- or ethyl-SO—, methyl- or ethyl-SO₂—,phenyl, benzyl, toluyl, xylyl, methylbenzyl, dimethylbenzyl,chlorophenyl, dichlorophenyl, methoxyphenyl, dimethoxyphenyl,methoxybenzyl, dimethoxybenzyl, CH₃—CO—, C₆H₅—CO—, CH₃—CO—O—,C₆H₅—CO—O—, CH₃—SO₂—O—, C₆H₅—SO₂—O—, —NH₂, —NHCH₃, —NHC₂H₅, NHC₈H₁₇,—N(CH₃)₂, —COOH, —CO—OCH₃, —CO—OC₂H₅, SO₃H, —SO₂—OCH₃, SO₂—OC₂H₅,—CO—NH₂, —CO—NCH₃, —CO—NHC₂H₅, —CO—NHC₈H₁₇, —CO—NH(CH₃)₂, —SO₂—NH₂,—SO₂—NHCH₃, —SO₂—NHC₂H₅, —SO₂—NHC₈H₁₇, —SO₂—N(CH₃)₂, H₂N—SO₂—,methoxymethyl, methoxyethyl, ethoxyethyl, —(OCH₂CH₂)₂—OH, —CN and —NO₂.

[0089] The number of substituents is arbitrary and depends essentiallyupon synthetic possibilities, the desired optical properties related tofluorescence and absorption, and the desired solubility.

[0090] In a preferred embodiment of the invention the compounds offormula I correspond to formula II,

[0091] wherein

[0092] R₇, R₈, R₉ and R₁₀ independently from one another can be H, F,Cl, Br, I, C₁ to C₁₈alkyl, C₁ to C₁₈alkoxy, C₁ to C₁₈alkylthio, aryl,aralkyl, C₁ to C₁₂alkyl-aryl or C₁ to C₁₂alkyl-aralkyl, and the ring 2is unsubstituted or substituted as described before, including thepreferred substituents.

[0093] Preferably at least one of R₇, R₈, R₉ and R₁₀ is one of thedefined substituents. More preferably R₈ and R₉ are one of the definedsubstituents. Mostly preferred R₇, R₈, R₉ and R₁₀ are substituents.

[0094] In the context of the invention when R₇, R₈, R₉ and R₁₀ meanlinear alkyl or branched alkyl they contain preferably 1 to 12 C-atoms,more preferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms andparticularly preferred 1 to 4 C-atoms. Some examples are methyl, ethyl,n- or i-propyl, n-, i- or t-butyl, and the isomers of pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl and octadecyl.

[0095] In the context of the invention when R₇, R₈, R₉ and R₁₀ meanlinear alkoxy or alkoxy branched they contain preferably 1 to 12C-atoms, more preferably 1 to 8 C-atoms, most preferably 1 to 6 C-atomsand particularly preferred 1 to 4 C-atoms. Some examples are methoxy,ethoxy, n- or i-propoxy, n-, i- or t-butoxy, and the isomers of pentoxy,hexoxy, heptoxy, octoxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy,tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxyand octadecyloxy.

[0096] In the context of the invention when R₇, R₈, R₉ and R₁₀ meanlinear alkylthio or alkylthio branched they contain preferably 1 to 12C-atoms, more preferably 1 to 8 C-atoms, most preferably 1 to 6 C-atomsand particularly preferred 1 to 4 C-atoms. Some examples are methylthio,ethylthio, n- or i-propylthio, n-, i- or t-butylthio, and the isomers ofpentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio,undecylthio, dodecylthio, tridecylthio, tetradecylthio, pentadecylthio,hexadecylthio, heptadecylthio and octadecylthio.

[0097] In the context of the invention R₇, R₈, R₉ and R₁₀ may be arylnaphthyl or preferably phenyl.

[0098] In the context of the invention R₇, R₈, R₉ and R₁₀ may be aralkylpreferably arylmethyl or -ethyl, wherein aryl means preferably phenyl ornaphthyl. Some examples are benzyl, phenylethyl and naphthylmethyl.

[0099] In the context of the invention when R₇, R₈, R₉ and R₁₀ arealkyl-aryl they are preferably alkylphenyl, more preferably C₁ toC₈alkylphenyl, and most preferably C₁ to C₄alkylphenyl. Some examplesare methylphenyl, ethylphenyl, n- or i-propylphenyl, n-, i- ort-butylphenyl, hexylphenyl, octylphenyl, dodecylphenyl, anddimethylphenyl.

[0100] In the context of the invention when R₇, R₈, R₉ and R₁₀ arealkyl-aralkyl they are preferably alkyl-benzyl, more preferably C₁ toC₈alkylbenzyl, and most preferably C₁ to C₄alkylbenzyl.

[0101] Some examples are methylbenzyl, ethylbenzyl, n- ori-propylbenzyl, n-, i- or t-butylbenzyl, hexylbenzyl, octylbenzyl,dodecylbenzyl, and dimethylbenzyl.

[0102] In an especially preferred embodiment of the invention the ring 2is also substituted, particularly in the 7-position, in the 8-positionor in both with in organic group substituent.

[0103] In a particularly preferred embodiment of the invention thecompounds of formula II corresponds to formula III,

[0104] wherein

[0105] R₇, R₈, R₉ and R₁₀ are Cl, phenyl or C₁ to C₁₂alkylphenyl,

[0106] R₁₁ is H or an organic group substituent, and

[0107] R₁₂ is H or an organic group substituent.

[0108] The ring 2 is preferably monosubstituted, meaning that one of R₁₁and R₁₂ is an organic group substituent.

[0109] Particularly preferred R₇, R₈, R₉ and R₁₀ are chlorine or phenyl.

[0110] In the context of the invention when R₁₁ or R₁₂ organic groupsubstituents they are preferably selected from the group consisting of—CN, —NO₂, —COOH, C₁ to C₁₈ alkyl, C₂ to C₁₈alkenyl, C₂ to C₁₈alkinyl,C₁ to C₁₈ hydroxyalkyl, C₁ to C₁₈ halogenalkyl, C₃ to C₁₂ cycloalkyl, C₆to C₁₈ aryl, C₃ to C₁₂ cycloalkyl-alkyl, C₆ to C₁₈ aralkyl, C₁ to C₁₈alkyloxy, C₃ to C₁₂ cycloalkyloxy, C₆ to C₁₈ aryloxy, C₃ to C₁₂cycloalkyl-alkyloxy, C₆ to C₁₈ aralkyloxy, C₁ to C₁₈ alkylthio, C₃ toC₁₂ cycloalkylthio, C₆ to C₁₈ arylthio, C₃ to C₁₂ cycloalkyl-alkylthio,C₆ to C₁₈ aralkylthio, C₁ to C₁₈ alkyl-CO—, C₃ to C₁₂ cycloalkyl-CO—, C₆to C₁₈aryl-CO—, C₃ to C₁₂ cycloalkylalkyl-CO—, C₆ to C₁₈ aralkyl-CO—,—NR₃R₄, alkoxyalkyl with 2 to 20 carbon atoms, polyoxyalkylene-OR₆,—X—(R₅)_(k)—C(O)—NR₃R₄, —X—(R₅)_(k)—C(O)—OR₆, —X—(R₅)_(k)—SO₂—OR₆,—X—(R₅)_(k)—SO₂—NR₃R₄, —NH—C(O)—R₆ and —O—C(O)—R₆,

[0111] wherein

[0112] R₃ and R₄ independently from one another can be H, C₁ toC₂₀alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl, C₁ to C₁₂alkylphenylor C₁ to C₁₂alkylbenzyl, or R₃ and R₄ together mean tetramethylene,pentamethylene, or the groups —CH₂—CH₂—O—CH₂—CH₂— or—CH₂—CH₂—NR₃—CH₂—CH₂—,

[0113] R₅ is C₁ to C₁₂alkylene, phenylene or benzylene,

[0114] R₆ means H, C₁ to C₂₀alkyl, cyclopentyl, cyclohexyl, phenyl,benzyl, C₁ to C₁₂alkylphenyl or C₁ to C₁₂alkylbenzyl,

[0115] X is a direct bond, —O— or S,

[0116] k is 0 or 1 and

[0117] and the salts of the acids.

[0118] The preferred meanings described before are also valid for themeanings of R₁₁, R₁₂, X and R₃ to R₆, when R₁₁ and R₁₂ are organic groupsubstituents they are most preferably selected from the group consistingof —CN, —NO₂, C₁ to C₁₈ alkyl, C₁ to C₁₈ hydroxyalkyl, C₅ to C₇cycloalkyl, C₆ to C₁₀ aryl, C₇ to C₁₁ aralkyl, C₁ to C₁₈ alkyloxy, C₃ toC₁₂ cycloalkyloxy, C₆ to C₁₀ aryloxy, C₅ to C₇ cycloalkyl-alkyloxy, C₇to C₁₁ aralkyloxy, C₁ to C₁₈ alkylthio, C₅ to C₇ cycloalkylthio, C₆ toC₁₀ arylthio, C₅ to C₇ cycloalkyl-alkylthio, C₇ to C₁₁ aralkylthio, C₁to C₁ alkyl-CO—, C₅ to C₇ cycloalkyl-CO—, C₆ to C₁₀aryl-CO—, C₅ to C₇cycloalkyl-alkyl-CO—, C₇ to C₁₁ aralkyl-CO—, —NR₃R₄, alkoxyalkyl with 2to 12 carbon atoms, polyoxyalkylene-OR₆, —X—(R₅)_(k)—C(O)—NR₃R₄,—X—(R₅)_(k)—C(O)—OR₆, —X—(R₅)_(k)—SO₂—OR₆, —X—(R₅)_(k)—SO₂—NR₃R₄,—NH—C(O)—R₆ and —O—C(O)—R₆,

[0119] wherein

[0120] R₃ and R₄ independently from one another mean H, C₁ to C₆alkyl,cyclopentyl, cyclohexyl, phenyl, benzyl, C₁ to C₆alkylphenyl or C₁ toC₆alkylbenzyl, or R₃ and R₄ together mean tetramethylene,pentamethylene, or the group —CH₂—CH₂—O—CH₂—CH₂—,

[0121] R₅ is C₁ to C₄alkylene, phenylene or benzylene,

[0122] R₆ means H, C₁ to C₁₂alkyl, cyclopentyl, cyclohexyl, phenyl,benzyl, C₁ to C₆alkylphenyl or C₁ to C₆alkylbenzyl,

[0123] X is a direct bond, —O— or S,

[0124] k is 0 or 1 and

[0125] and the salts of the acids.

[0126] In an especially preferred embodiment of the invention R₁₁ andR₁₂ are selected from the group consisting of —NO₂, C₁ to C₁₈ alkyl,which is linear or branched, C₁ to C₁₈ alkyloxy, which is linear orbranched, —C(O)OH, or —C(O)—O—C₁ to C₁₈alkyl.

[0127] The compounds of formula I to III are partially known or can beeasily prepared from unsubstituted or substituted orthophenylenediaminesand from unsubstituted or substituted phthalic anhydride as for exampledescribed in EP-A-0 456 609.

[0128] The guest chromophore can be selected from a broad range ofpigments, pigment derivatives, dyes and their derivatives and mixturesthereof, so long as they are luminescent in the molecular state, andtheir absorption spectra do overlap with the emission spectrum of thehost chromophore. Some guest chromophores are for example described inWO 93/23492.

[0129] In one embodiment of this invention, the guest chromophorepreferably is soluble, at least to some extent, in a solvent, and—ifdesired—in the host chromophore, allowing formation of homogeneous solidsolutions.

[0130] Solubility of a guest chromophore means in the context of theinvention that at least 200 mg, more preferably at least 300 mg and mostpreferably at least 500 mg of the guest chromophore are soluble in 1liter of solvent like dimethylformamide at 20° C. This definitionemploys also to compositions where the host and guest chromophores areembedded in a polymer matrix.

[0131] The guest chromophore may be selected from the group consistingof quinacridones, perylenes, perinones, diketo- anddithioketopyrrolopyrroles, rhodamines, coumarins, xanthens, oxazines,oxazoles, cyanines, phthalocyanines, porphyrines, styryl dyes, metalcomplexes and mixtures thereof.

[0132] Preferred guest chromophores are selected from group consistingof quinacridones, perylenes, perinones, diketopyrrolopyrroles,rhodamines, coumarins, cyanines, phthalocyanines, porphyrines, styryldyes and mixtures thereof. Especially preferred are quinacridones,perylenes, diketopyrrolopyrroles, rhodamines, coumarins and mixturesthereof.

[0133] The guest compounds and their derivatives are well known in theart or can be prepared by analogous processes.

[0134] Quinacridones can be found described in Chemical Reviews 67 (1)pages 1 to 18 (1967).

[0135] The quinacridones may correspond to the formula VII

[0136] wherein

[0137] R₂₆ to R₂₉ and R₃₂ to R₃₅ independently from one another can beH, C₁ to C₆alkyl, C₁ to C₆alkoxy, F, Cl, Br, CN, NO₂, or —NR₂₁R₂₂,wherein R₂₁ and R₂₂ independently from one another are H, C₁ toC₂₀alkyl, phenyl, C₁ to C₁₂alkylphenyl, benzyl or C₁ to C₁₂alkylbenzyl,or R₂₁ and R₂₂ together mean tetramethylene, pentamethylene or—CH₂CH₂—O—CH₂CH₂—; or two neighbored residues of R₂₆ to R₂₉ and/or R₃₂to R₃₅ together with carbon atoms, to which they are linked, a 5- or6-membered aliphatic, heteroaliphatic, aromatic or heteroaromatic ring,whereby the heteroatoms are selected from the group of —O—, —S— and N;and

[0138] R₃₀ and R₃₁ independently from one another are H, C₁ to C₁₈alkyl,C₂ to C₁₈alkenyl, C₂ to C₁₈alkinyl, phenyl, benzyl, C₁ to C₆alkylphenyl,C₁ to C₆alkylbenzyl or R₃₆—O—C(O)—, wherein R₃₆ means C₁ to C₁₈alkyl, C₂to C₁₈alkenyl, C₂ to C₁₈alkinyl, phenyl, benzyl, C₁ to C₆alkylphenyl, orC₁ to C₆alkylbenzyl.

[0139] Perylenes can be found described in U.S. Pat. Nos. 4,446,324 and5,470,502. Preferred examples are those perylenes of formulae IX and X,

[0140] wherein

[0141] R₃₇ and R₃₈ independently from one another can be F, Cl, Br, orCN,

[0142] R₃₉ and R₄₀ independently from one another mean R₃₆—O—C(O)—,wherein R₃₆ means C₁ to C₁₈alkyl, C₂ to C₁₈alkenyl, C₂ to C₁₈alkinyl,phenyl, benzyl, C₁ to C₆alkyl phenyl, or C₁ to C₆alkylbenzyl.

[0143] R₄₁ and R₄₂ independently from one another can be H, C₁ toC₁₈alkyl, C₂ to C₁₈alkenyl, C₂ to C₁₈alkinyl, phenyl, benzyl, C₁ toC₆alkylphenyl, C₁ to C₆alkylbenzyl or R₃₆—O—C(O)—, wherein R₃₆ means C₁to C₁₈alkyl, C₂ to C₁₈alkenyl, C₂ to C₁₈alkinyl, phenyl, benzyl, C₁ toC₆alkylphenyl, or C₁ to C₆alkyl benzyl, and

[0144] the R₄₃ independently from one another are C₁ to C₁₈alkoxy,phenoxy or C, to C₁₂alkylphenoxy.

[0145] Some examples are the commercially available compounds are shown;

[0146] Diketo- and dithioketopyrrolopyrroles can be found described inU.S. Pat. No. 4,415,685 and JP-A-61 162 555.

[0147] Examples for diketopyrrolopyrroles correspond to the formula XI,

[0148] wherein

[0149] the R₄₄ independently from one another are H, halogen, or phenylwhich is unsubstituted or substituted with C₁ to C₆alkyl, C₁ toC₆alkoxy, phenyl, C₁ to C₄alkylphenyl, F, Cl, Br, CN, NO₂, or —NR₂₁R₂₂,wherein R₂₁ and R₂₂ independently from one another are H, C₁ toC₂₀alkyl, phenyl, C₁ to C₁₂alkylphenyl, benzyl or C₁ to C₁₂alkylbenzyl,or R₂₁ and R₂₂ together mean tetramethylene, pentamethylene or—CH₂CH₂—O—CH₂CH₂—; and

[0150] the R₄₅ independently from one another mean H, C₁ to C₁₈alkyl, C₂to C₁₈alkenyl, C₂ to C₁₈alkinyl, phenyl, benzyl, C₁ to C₆alkyl phenyl,or C₁ to C₆alkylbenzyl, or R₃₀—O—C(O)—, wherein R₃₀ means C₁ toC₁₈alkyl, C₂ to C₁₈alkenyl, C₂ to C₁₈alkinyl, phenyl, benzyl, C₁ toC₆alkylphenyl, or C₁ to C₆alkyl benzyl.

[0151] A range of commercial rhodamines are available from ACROSORGANICS catalogue of fine chemicals Vol. 1 (1996).

[0152] Preferred examples of rhodamines are those of the formula XII,

[0153] wherein

[0154] wherein R₂₁ and R₂₂ independently from one another are H, C₁ toC₂₀alkyl, phenyl, C₁ to C₁₂alkylphenyl, benzyl or C₁ to C₁₂alkylbenzyl,or R₂₁ and R₂₂ together mean tetramethylene, pentamethylene or—CH₂CH₂—O—CH₂CH₂—;

[0155] R₄₆ means H, C₁ to C₁₈alkyl, C₂ to C₁₈alkenyl, C₂ to C₁₈alkinyl,phenyl, benzyl, C₁ to C₆alkyl phenyl, or C₁ to C₆alkylbenzyl, or anequivalent of a metal or ammonium cation;

[0156] and R₄₇ means the group ═NR₄₈, or the group ═⁺NR₄₈R₄₉X⁻, R₄₈ andR₄₉ independently from one another are H, C₁ to C₁₈alkyl, phenyl, C₁ toC₁₂alkylphenyl, benzyl or C₁ to C₁₂alkylbenzyl; and X is monovalentanion.

[0157] A range of commercial coumarins, oxazines, cyanines, xanthens andstyryl dyes are available from ACROS ORGANICS catalogue of finechemicals Vol. 1 (1996). A range of commercial oxazoles are availablefrom DOJINDO LABORATORIES catalogue 18th edition (1992).

[0158] Porphyrines and phthalocyanines are for example described in abook “The Phthalocyanines” (Frank H. Moser et. al., published byFranklin, 1983).

[0159] In the context of the invention, effective amount of a guestchromophore means for example, that the composition may contain from0.001 to 30, preferably from 0.01 to 20, more preferably from 0.01 to 10and most preferably from 0.01 to 5 percent by weight, of guestchromophore, related to the total amount of host and guest chromophore.

[0160] Further, in the context of this invention, the meaning of theoverlap of the absorption spectrum of the guest chromophore with thefluorescence emission spectrum of the host chromophore, is clear to askilled person in this field. However, to facilitate the understandingto others, overlap means “spectral overlap” defined by the followingintegral

S=∫ ₀ ^(+∞) f _(F)(v)f _(A)(v)dv

[0161] wherein f_(F)(v) is normalized, so that ∫₀ ^(+∞)f_(F)(v)dv isequal to fluorescence quantum yield of the host, and where v is the wavenumber, f_(F) the fluorescence spectrum of the host measured in quanta,and f_(A) the spectral distribution of the molar extinction coefficientof the guest. The spectral overlap to realize photoluminescenceenhancement usually is greater than 10, preferably greater than 100,more preferably greater than 500. An upper limit makes no sense, becausethe quantity “overlap” has no maximum (i.e. the larger, the better)).

[0162] In the context of this invention, embedded means a distributionof the guest chromophore (or both host and guest chromophore, if apolymer matrix is used) within the matrix or total amount of hostchromophore (or—accordingly, of course, the polymer matrix). Preferably,this distribution is homogeneously. Hence, in another preferredembodiment of this invention, (a) the guest chromophore is homogeneouslydistributed within the matrix of the host chromophore, or (b) the hostchromophore and the guest chromophore both are homogeneously distributedwithin the polymer matrix.

[0163] In the context of this invention, the term “homogeneously” meansthat the components within the matrix, e.g. the guest chromophore, isevenly or uniformly distributed or dispersed throughout the matrix (orhost or host/polymer matrix), and, preferably in the ideal case areessentially equidistant from each other. According to observationstoday, the more even or uniform the distribution is, the better are thefluorescence properties, because the coexistence of areas having brightand weak fluorescence are reduced as well as areas wherein the emissioncolor is closer to that of the host than the guest. Furthermore, ahomogeneous or even distribution is preferred, because usually thechances for aggregation are decreased.

[0164] In another preferred embodiment of this invention, the averageparticle size of the guest chromophores (or the host and guestchromophores, if a polymer matrix is applied) are not bigger than adesired diameter, preferably more than a desired amount of the guestchromophores (or host and guest chromophores, if a polymer matrix isapplied) are in their molecular state. Most preferably, the guestchromophores (or host and guest chromophores, if a polymer matrix isapplied) are molecularly dissolved and homogeneously distributed withinthe matrix of the host chromophore (or the polymer matrix).

[0165] In the context of this invention, the term “dissolved” means thata molecule exists as a free and isolated entity in a given matrix,preferably in such a way, that it is disengaged from any interactionsbetween molecules of the same species, i.e. it is entirely surrounded bymatrix molecules. Usually the matrix can be a liquid organic solvent ora solid material such as a polymer or another fluorescent material(host), which possesses a different chemical structure. Theconcentration limits for molecules in the dissolved state in generaldepend strongly on the associative nature between the molecule and thematrix medium, and/or the intrinsic cohesive forces that exist betweenthe guest molecules in question. Correspondingly, it is impossible todefine universal ranges for preferred concentrations, and therefore,usually must be treated on an ad hoc basis, e.g. by a few simpleexperiments.

[0166] Polymers which may be used as polymer matrix may be selected fromthermoplastics, polymer blends, thermosettings and structurallycrosslinked polymers. The polymers may be homopolymers, copolymers,blockpolymers, graft polymers or random polymers.

[0167] The polymers may be opaque or translucent but preferablytransparent. The polymers may be selected for example from the group ofthermoplastic polymers like polyesters, poly amides, polyimides,polyamide-imides, polyamide esters, polyurethanes, polyureas,polyolefines; polymers from substituted olefines like vinylethers,vinylesters, vinylalcohols, vinylchloride, vinyldichloride,acetonitrile, acrylic acid, methacrylic acid, esters and amides ofacrylic acid and methacrylic acid, styrene, chlorostyrene,methylstyrene, styrene sulfonic acid and their esters and amides,vinylcarbazole, vinylpyridine, vinylpyrrolidone: polymaleic acid andesters and amides therefrom; polyethers (for example from bisphenol-Adiglycidyl ether), polysulfones, polyketones, polyphenylsulfides, andpolyacetales; and natural polymers and their derivatives like celluloseand its esters and ethers, and starch or derivatives of starch.

[0168] Examples of thermosetting resins and structurally crosslinkedresins are polyepoxides, unsaturated polyesters, photocrosslinked resinsfor example from acrylic acid and/or methacrylic esters and/or amidesfrom polyols and/or polyamines, melamine/formaldehyde resins, andphenol/formaldehyde resins; polymers from butadiene, isoprene and orchloroprene and copolymers with olefins, which may be crosslinked and ofrubbery nature, including latices; as well as silicates obtainablethrough the known sol/gel process.

[0169] The polymeric compositions of the invention may contain furtheringredients to enhance certain features such as electrical, physical andmechanical properties, and/or the processability, for example dispersingagents to achieve a uniform distribution of particles, lubricants,plasticizers, antistatica, solvents, molding agents, antioxidants, lightstabilizers, fillers and reinforcing fillers like glass balls and glassfibers, silicates (e.g. mica, clay, wollastonite), metal andsemiconductor metal oxides, metal carbonates, metal salts, metals andsemiconductor metals, carbon black, as powder, or carbon fibers,whiskers, metal and semiconductor metal carbides, metal andsemiconductor metal nitrides, dyes, pigments and others.

[0170] The weight ratio of (host chromophores plus guestchromophores):polymer matrix is dependent on the actual practicalapplication, hence there are no well defined preferred ratios, otherthan the broad range 99:1 to 1:999. In certain applications where bothcolor strength and fluorescence are required, then the preferred ratiosof the chromophores to the polymer matrix are 20:80 to 99:1, preferably50:50 to 99:1 and more preferably 80:20 to 99:1. In circumstances wherefluorescence is desired but color strength is not required, then thepreferred ratio of the chromophores to the polymer matrix are 20:80 to1:999, more preferably 10:90 to 1:999 and more preferably 5:95 to 1:999.

[0171] The composition according to the invention can be prepared usingknown processes like co-sublimation, as described in JP-A-03 255 190, ornew processes that utilize the solubility of the guest chromophores.

[0172] A further embodiment of the invention is a process for thepreparation of the inventive, abovementioned composition, comprising ahost chromophore and a guest chromophore and, if desired, a polymermatrix, wherein the absorption spectrum of the guest chromophoreoverlaps with the fluorescence emission spectrum of the hostchromophore, characterized in

[0173] (a) selecting the host chromophore from the group consisting ofbenzo[4,5]imidazo[2,1-a]isoindol-11-ones,

[0174] (b) mixing the host chromophore and an effective amount of atleast one guest chromophore, and optionally a polymer or polymerisableprecursor, in the presence of a solvent, and

[0175] c) then precipitating the host and guest chromophores, optionallyin the presence the polymer of step (b), or (d) precipitating the hostand guest chromophores during polymerization of the polymer precursor ofstep (b).

[0176] In the context of the invention mixing of the materials can beachieved through dissolution of the components in a common solvent andfollowed by the subsequent evaporation of the solvent; precipitationfrom a good solvent into a poor solvent (vigorous stirring can beapplied); freeze-drying; and precipitation during polymerization ofpolymerizable monomers or oligomers, preferably under vigorous stirring.

[0177] Suitable inert solvents are for example protic-polar and aproticsolvents, which may be used alone or in an admixture of at least twosolvents. Examples are: water, alcohols (methanol, ethanol, propanol,butanol), ethyleneglycolmonomethyl- or -monoethylether, ethers(dibutylether, tetrahydrofuran, dioxane, ethyleneglycol dimethylether,ethyleneglycoldiethylether, diethyleneglycoldiethylether,triethyleneglycoldimethylether), halogenated hydrocarbons(methylenchloride, chloroform, 1,2-dichloroethane,1,1,1-trichlororethane, 1,1,2,2-tetrachloroethane), carboxylic estersand lactones (acetic acid ethylester, propionic acid methylester,benzoic acid ethylester, 2-methoxyethylacetate, γ-butyrolactone,δ-valerolactone, pivalolac tone), carboxylic acid amides and lactames;N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide,tetramethylurea, hexamethylphosphorous acidtriamide, γ-butyrolactame,ε-caprolactame, N-methylpyrrolidone, N-acetylpyrrolidone,N-methylcaprolactame; sulfoxides (dimethylsulfoxide), sulfones(dimethylsulfone, diethylsulfone, trimethylenesulfone,tetramethylenesulfone), tertiary amines (N-methylpiperidine,N-methylmorpholine), aliphatic and aromatic hydrocarbons likepetroleumether, pentane, hexane, cyclohexane, methylcyclohexane, benzeneor substituted benzenes (chlorobenzol, o-dichlorobenzene,1,2,4-tri-chlorobenzene, nitrobenzene, toluene, xylene) and nitrites(acetonitrile, propionitrile, benzenenitrile, phenylacetonitrile),ketones (acetone, methyl-isobutyl-ketone).

[0178] The coprecipitation may be carried out in by a number of methods.When the host and guest chromophores possess solubilities affording thedesired weight range in the final composition, the precipitation may becompleted by adding the solution to a non-solvent, filtering off thenthe precipitate and removing the solvent, preferably in drying the solidat elevated temperatures and preferably under vacuum. Anotherpossibility is to simply evaporate the solvent under vacuum and/orelevated temperatures.

[0179] In the process of freeze-drying, a steady state of components andsolvent in general is generated by freezing a solution, wherein thecomponents are in homogeneous distribution. This state is maintainedupon removal of the solvent by freeze-drying. The furnished materialsare usually highly fluorescent and exhibit all the featurescharacteristic of host/guest materials.

[0180] In another preferred embodiment the host and guest chromophoresare dissolved in a suitable solvent, and then this solution is added toa polymer gel (polymer swollen with a solvent). Usually the host andguest chromophores are in turn soaked into the gel. As a rule, removalof the solvent and drying generates a composition according to theinvention.

[0181] In another preferred embodiment host and guest chromophores aremilled together using a ball mill. Due to the high shearing forcesusually the guest chromophore particles and/or molecules penetrate intothe host chromophore matrix, forming a fluorescent composition accordingto the invention.

[0182] In another preferred embodiment the host and guest chromophoresare mixed, optionally together with a polymer, and then melt-mixed attemperatures below the respective decomposition temperatures of theindividual components.

[0183] The compositions on hand can span a broad number of applications.For example, the inventive compositions could be rendered very useful ascoloring agents in applications such as road markings and traffic signsfor night and daylight uses, as they exhibit brilliant daylightfluorescence and can also be excited by the UV radiation of motorvehicles halogen lamps, thereby providing intense, bright colors duringboth day and nighttime. Other applications include their use aspigments, coloring agents, materials for scintillators, materials forsolar energy collectors, materials for light emitting electroluminescentdevices, materials for generating fluorescent images. Moreover, thechoice of guest compound can lend a lot of flexibility to the desiredemission wavelength required of the overall system, therein impartingthe capability for color-tuning and ease of tailoring of the core systemto specific color applications via wavelength modulation. It is alsopossible to produce fluorescent images (high relief structures) by thewell known photoresist technology. The compositions of the invention mayalso be used in paints, lacquers and printing inks.

[0184] The compositions according to the invention may be used invarious forms depending upon the end use purpose.

[0185] The compositions according to the invention may be milled togenerate a powdery form for industrial applications.

[0186] Another embodiment of the invention is a composition according tothe invention in form of a powder, which contains particles. Theparticles may have an average diameter from 10 nm to 500 μm, morepreferably 50 nm to 100 μm and most preferably 50 nm to 50 μm. Thepowders also include polymer particles containing the host and guestchromophores dissolved and uniformly distributed therein, and can beobtained via grinding or emulsion polymerization, or both.

[0187] The particles of the composition of the invention may beencapsulated with polymers by known methods to generate for examplepigments for coloring polymers. The compositions according to theinvention may be used as a coating to form a layer on support materials,preferably via a process of co-sublimation. A further embodiment of theinvention is a support material to which on at least partially is coateda layer of the composition according to the invention.

[0188] Suitable support (or carrier) materials may be selected from thegroup consisting of organic or inorganic materials like glass, ceramics,minerals, plastics, paper, wood, semiconductors, metals, metal oxidesand semiconductor metal oxides, and metal or semiconductor metalnitridesor -carbides.

[0189] The thickness of the layer depends on the desired use and usuallymay be from 0.01 to 1000 μm, preferably 0.05 to 500 μm, and especiallypreferred 0.1 to 100 μm.

[0190] The coatings may be protected by covering coatings whichpreferably are transparent. Such coatings are well known, in particularphotocrosslinked coatings are useful for this purpose, and are wellknown in the art.

[0191] The powders according to the invention may be admixed withpolymers. A further embodiment of the invention is a compositioncomprising (a) a polymer substrate, and (b) particles of the compositionaccording to the invention, homogeneously distributed therein.

[0192] The amount of the particles may be for example 0.0001 to 90weight %, preferably 0.1 to 90 weight % and more preferably 1 to 50weight % of the total composition.

[0193] The polymer substrate may be selected from thermoplastics,polymer blends, thermosettings and structurally crosslinked polymers.The polymers may be homopolymers, copolymers, blockpolymers, graftpolymers or random polymers.

[0194] The polymers may be opaque or translucent but preferablytransparent. The polymers may be selected for example from the group ofthermoplastic polymers like polyesters, polyamides, polyimides,polyamide-imides, polyamide esters, polyurethanes, polyureas,polyolefines; polymers from substituted olefines like vinylethers,vinylesters, vinylalcohols, vinylchloride, vinyldichloride,acetonitrile, acrylic acid, methacrylic acid, esters and amides ofacrylic acid and methacrylic acid, styrene, chlorostyrene,methylstyrene, styrene sulfonic acid and their esters and amides,vinylcarbazole, vinylpyridine, vinylpyrrolidone: polymaleic acid andesters and amides therefrom; polyethers (for example from bisphenol-Adiglycidyl ether), polysufones, polyketones, polyphenylsulfides, andpolyacetales; and natural polymers and their derivatives like celluloseand its esters and ethers, and starch or derivatives of starch.

[0195] Examples of thermosetting resins and structurally crosslinkedresins are polyepoxides, unsaturated polyesters, photocrosslinked resinsfor example from acrylic acid and/or methacrylic esters and/or amidesfrom polyols and/or polyamines, melamine/formaldehyde resins, andphenol/formaldehyde resins; polymers from butadiene, isoprene and orchloroprene and copolymers with olefins, which may be crosslinked and ofrubbery nature; as well as silicates obtainable for example through theknown sol/gel process.

[0196] The thermoplastic compositions are for example obtainable byknown mixing methods like admixing solutions of polymers and removingthe solvent, injection molding and extrusion molding. Thermosetting andstructurally crosslinked compositions are obtainable by known methodslike press molding, whereby the particles usually are dispersed prior tothe polymerization of a precursor composition.

[0197] The polymeric compositions of the invention may contain furtheringredients to enhance certain features such as electrical, physical andmechanical properties, and/or the processability, for example dispersingagents to achieve a uniform distribution of particles, lubricants,plasticizers, antistatica, solvents, molding agents, antioxidants, lightstabilizers, fillers and reinforcing fillers like glass balls and glassfibbers, silicates (e.g. mica, clay, wollastonite), metal andsemiconductor metal oxides, metal carbonates, metal salts, metals andsemiconductor metals, carbon black, as powder, or carbon fibers,whiskers, metal and semiconductor metal carbides, metal andsemiconductor metal nitrides, dyes, pigments and others.

[0198] The polymer compositions of the invention me be used in the formof shaped articles.

[0199] The polymer composition or a polymerisable precursor compositionwith host/guest particles may contain a solvent to generate coatingcompositions. Suitable solvents are mentioned before.

[0200] In another aspect of the invention the polymer compositioncontaining particles of the host/guest composition or particles frompolymers and dissolved host/guest chromophores may be used as coatingson carrier materials, using the above mentioned composition.

[0201] Another embodiment of the invention is a composition comprising(a) a carrier material and (b) at least on one surface a coating of acomposition comprising (a) a polymer substrate, and (b) particles of thecomposition, or particles from polymers and dissolved host/guestchromophores, or both according to the invention, homogeneouslydistributed therein.

[0202] In another aspect of the invention the composition containing apolymer and soluble host/guest chromophores may be used as coatings oncarrier materials, using a solution of said composition.

[0203] Another embodiment of the invention is a composition comprising(a) a carrier material and (b) at least on one surface a coating of acomposition comprising (a) a polymer matrix, and (b) a polymer andsoluble host/guest chromophores according to the invention,homogeneously distributed therein.

[0204] Suitable carrier materials may be selected from organic orinorganic materials like glass, ceramics, minerals, plastics, paper,wood, textiles, semiconductors, metals, metal oxides and semiconductormetal oxides, and metal or semiconductor metal-nitrides or -carbides.

[0205] The thickness of the coating depends on the desired use and maybe from 0.01 to 1000 μm, preferably 0.05 to 500 μm, and especiallypreferred 0.1 to 100 μm.

[0206] The coatings may be protected by covering coatings whichpreferably are transparent. Such coatings are well known, in particularphotocrosslinked coatings are useful for this purpose, and are wellknown in the art.

[0207] The coated materials are obtainable by known methods likepainting, casting or spincoating, directly or with dispersion of thepolymeric compositions.

[0208] It is also possible to use a polymerisable composition containingpolymer forming monomers or oligomeric precursors, in particularcrosslinkable olefinically unsaturated monomers are useful in generatingsuch coatings. The polymerization may be induced thermally or by actinicradiation or both. It is often preferred to carry-out thepolymerisations in the presence of a radical initiator species. Thecoating compositions are novel and a further embodiment of theinvention.

[0209] A further embodiment of the invention is a solvent containingliquid composition, comprising

[0210] (1) a soluble polymer, and

[0211] (2) particles of the host and guest chromophore of a compositionaccording to the invention, or dissolved therein host and guestchromophores according to the invention.

[0212] These compositions may contain a solvent, such as those mentionedbefore, and optionally surfactants and dispersing agents. The viscosityrange of the composition depends on the desired application, and can bereadily by choice of solvent quantity, polymers binder and fluorescentmaterials. To further achieve a desired viscosity thickening agents mayadditionally be used. Suitable solvents have been mentioned.

[0213] The preparation of this composition can be achieved by simplymixing the ingredients together using suitable mixing equipment.Dispersions are in general stable depending upon the viscosity.Aggregated particles may be redistributed by stirring.

[0214] In a highly advantageous embodiment of preparing coatingspolymerisable compositions can be used, wherein at least one surface ofa carrier material is coated and subsequently polymerized by heat,radiation or both. Photopolymerizable mixtures can also be used togenerate fluorescent images by known photoresist technology.

[0215] A further embodiment of the invention is a polymerisablecomposition comprising polymerisable monomers or prepolymers inadmixture with a composition according to the invention in the form of apowder containing particles, or with host and guest chromophoresaccording to the invention, preferably dissolved therein, or both.

[0216] The composition may be used to generate the polymers or polymerparticles according to the invention as described before. Preferably thecomposition contains a solvent, when coatings or images are to begenerated. The afore described embodiments also apply to thiscomposition, inclusive of the preferred embodiments.

[0217] In a preferred embodiment the composition is based onpolymerisable monomers and/or prepolymers containing a group selectedfrom olefinically unsaturated groups, preferably from —CH═CH₂ and—C(CH₃)═CH₂, which can be thermally or photo-polymerized.

[0218] Photopolymerisable monomers and prepolymers are well known in theart and described for example in EP-A-0 654 711. Preferredphotopolymerisable monomers and prepolymers are those based on theesters or amides of acrylic acid or methacrylic acid and alcohols,polyols, amines and polyamines.

[0219] Preferred ethylenically unsaturated photopolymerisable agents areselected from the group of acrylic or methacrylic acid esters ofaliphatic, cycloaliphatic and cycloaliphatic-aliphatic alcohols anddiols to tetrols, and amines and diamines to tetramines containingespecially preferred 2 to 12, and particularly preferred 2 to 8 C-atoms.Some examples of these diols are alkylenediols like ethylenglycol, 1,2-or 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, pentanediol,hexanediol, octanediol, decanediol, dodecanediol, cyclohexanediol,di(hydroxymethyl)-cyclohexane, polyoxyalkylendiols from preferablyC₂-C₆alkylendiols with preferably 2 to 100 alkylenediol units, morepreferably 2 to 50 alkylenediol units, and most preferably 2 to 20alkylenediol units, like for example polyethylenediols,polypolypropylenediols, polybutylenediols and polyethylene/polypropylenediols, further 1,1,1-trihydroxymethylethane or -propane,pentaerythritol and dipentaerythritol. Some examples for polyamines areethylenediamine, 1,3- and 1,3-propanediamine, 1,2-, 1,3- and1,4-butanediamine, 1,6-hexanediamine, diethylenetriamine,triethylenetetramine, cyclohexanediamine, (aminomethyl)cyclohexaneamine,isophorondiamine and di(aminomethyl)cyclohexane. Examples of alcoholsare linear or branched C₁ to C₂₀alkanols.

[0220] The photopolymerisable composition may be particularly suitablefor generating coatings and images.

[0221] A further embodiment of the invention is a composition comprisinga carrier material with a high relief image of a polymerized photoresistmaterial, which contains a composition according to the invention in theform of a powder containing particles, or host and guest chromophoresaccording to the invention, or both, if desired dissolved and/orhomogeneoulsly distributed therein.

[0222] A further embodiment of the invention is a process for thepreparation of fluorescent high relief images on a carrier. Preferably,this involves irradiating under a mask or by laser writing, the abovecoated photopolymerisable composition (which preferably has been driedand removed of solvent) on the carrier, developing the irradiatedcomposition and finally removing the non-irradiated parts.

[0223] Removal of the non-irradiated parts in general is mostly carriedout by treatment with solvent.

[0224] All highly fluorescent materials described before can broadly beused in optical and electrooptical devices.

[0225] A further embodiment of the invention is a process for thecreation of fluorescent radiation which requires the excitation eitherelectrically or by UV or visible radiation, or both, of a fluorescentcomposition according to the invention.

[0226] Another embodiment of the invention is the use of thecompositions according to the invention as fluorescent materials.

[0227] As described before benzo [4,5] imidazo [2,1-a] isoindol-11-one,1,2,3,4-tetrachloro-benzo [4,5] imidazo [2,1-a] isoindol-11-one and somesubstituted derivatives are known in the art. From our investigations itwas found that benzo [4,5] imidazo [2,1-a] isoindol-11-ones and1,2,3,4-tetrachloro-benzo [4,5] imidazo [2,1-a] isoindol-11-ones showvery high light stabilities, as measured by a time dependent exposuretesting. Furthermore, it was found that the light stability of thesecompounds is reduced by substitution in the 7- and/or 8-positions. Inthe case of 1,2,3,4-tetraphenyl-benzo [4,5] imidazo [2,1-a]isoindol-11-one, it exhibits a moderate light stability, which sufficesfor a number of applications. However it was found, that the solid stateluminescence is maintained, the light stability is greatly improved, andthe compounds have a desired solubility, when the benzo [4,5] imidazo[2,1-a] isoindol-11-one is substituted in the 1-, 2-, 3- and/or4-positions and in the 7- and/or 8-positions with selected substituents.

[0228] A further embodiment of the invention a compound of the formulaV,

[0229] wherein

[0230] at most three of R₁₃, R₁₄, R₁₅ and R₁₆ are H and at least one ofR₁₃, R₁₄, R₁₅ and R₁₆ are a substituent selected from the group of C₁ toC₁₈alkyl, C₁ to C₁₈alkoxy, C₁ to C₁₈alkylthio, C₁ to C₁₂alkoxy-polyC₂ toC₆oxyalkylene; unsubstituted or with F, Cl, Br, —CN, C₁ to C₁₂alkyl, C₁to C₁₂alkoxy, C₁ to C₁₂alkylthio, or —NR₂₁R₂₂ substituted C₅ toC₈cycloalkyl, C₅ to C₈cycloalkoxy, C₅ to C₈cycloalkylthio, C₅ toC₈cycloalkyl-C₁ to C₄alkyl, C₅ to C₈cycloalkyl-C₁ to C₄alkoxy, C₅ toC₈cycloalkyl-C₁ to C₄alkylthio, phenyl, phenyloxy, phenylthio, phenyl-C₁to C₄alkyl, phenyl-C₁ to C₄alkoxy, phenyl-C₁ to C₄alkylthio; or

[0231] R₁₃ and R₁₄ together, R₁₅ and R₁₆ together, or R₁₃ and R₁₄together and R₁₅ and R₁₆ together, or R₁₄ and R₁₅ together are selectedfrom the groups —CH═CR₂₄—CR₂₅═CH—, —N═CR₂₄—CR₂₅═CH—, —CH═CR₂₄—CR₂₅═N—,—CH═N—CR₂₅═CH—, —CH═CR₂₄—N═CH—, —N═CR₂₄—CR₂₅═N—, —N═CR₂₄—N═CH—,—CH═CH—O—, —CH═CH—S—, —CH═CH—NR₂₃—;

[0232] R₁₇ and R₂₀ independently from one another are H or have themeaning of R₁₈; one of R₁₈ and R₁₉ are H and the other of R₁₈ and R₁₉ orboth are a substituent selected from the group of C₁ to C₁₈alkyl, C₁ toC₁₈alkoxy, C₁ to C₁₈alkylthio, C₁ to C₁₂alkoxy-polyC₂ to C₆oxyalkylene;unsubstituted or with F, Cl, Br, —CN, C₁ to C₁₂alkyl, C₁ to C₁₂alkoxy,C₁ to C₁₂alkylthio, or —NR₂₁R₂₂ substituted C₅ to C₈cycloalkyl, C₅ toC₈cycloalkoxy, C₅ to C₈cycloalkylthio, C₅ to C₈cycloalkyl-C₁ to C₄alkyl,C₅ to C₈cycloalkyl-C₁ to C₄alkoxy, C₅ to C₈cycloalkyl-C₁ to C₄alkylthio,phenyl, phenyloxy; phenylthio, phenyl-C₁ to C₄alkyl, phenyl-C₁ toC₄alkoxy, phenyl-C₁ to C₄alkylthio, phenyl-C₂ to C₁₂alkylidene,phenyl-C(O)—, phenyl-NR₂₃—C(O)—, phenyl-NR₂₃—S(O)₂—, phenyl-S(O)—,phenyl-S(O)₂—, phenyl-CO₂—, phenyl-S(O)—O—, phenyl-SO₃—, phenyl-NR₂₃—,or phenyl-CH═CH—; or

[0233] R₁₇ and R₁₈ together, R₁₉ and R₂₀ together, or R₁₇ and R₁₈together and R₁₉ and R₂₀ together, or R₁₈ and R₁₉ together are selectedfrom the groups —CH═CR₂₄—CR₂₅═CH—, —N═CR₂₄—CR₂₅═CH—, —CH═CR₂₄—CR₂₅═N—,—CH═N—CR₂₅═CH—, —CH═CR₂₄—N═CH—, —N═CR₂₄—CR₂₅═N—, —N═CR₂₄—N═CH—,—CH═CH—O—, —CH═CH—S—, —CH═CH—NR₂₃—;

[0234] R₂₁ and R₂₂ are independently from one another are C₁ toC₂₀alkyl, phenyl, C₁ to C₁₂alkylphenyl, benzyl or C₁ to C₁₂alkylbenzyl,or R₂₁ and R₂₂ together mean tetramethylene, pentamethylene or—CH₂CH₂—O—CH₂CH₂—;

[0235] R₂₃ is H C₁ to C₄alkyl or benzyl; and

[0236] R₂₄ and R₂₅ are independently from one another H, C₁ to C₆alkyl,C₁ to C₆alkoxy, C₁ to C₆alkylthio, or F, Cl or Br.

[0237] In a preferred embodiment R₁₃ and R₁₄ are substituents, and mostpreferably R₁₃, R₁₄, R₁₅ and R₁₆ are substituents. In still anotherpreferred embodiment, R₁₃ and R₁₄, R₁₅ and R₁₆, R₁₄ and R₁₅, or R₁₃ andR₁₄ and R₁₅ and R₁₆ each together mean —CH═CR₂₄—CR₂₅═CH—,—N═CR₂₄—CR₂₅═CH—, —CH═CR₂₄—CR₂₅═N—, —CH═N—CR₂₅═CH—, —CH═CR₂₄—N═CH—.

[0238] In an other preferred embodiment R₁₇ and R₂₀ mean H, and R₁₇ andR₁₉ or both are substituents. In still another preferred embodiment, R₁₇and R₁₈, R₁₉ and R₂₀, R₁₈ and R₁₉, or R₁₇ and R₁₈ and R₁₉ and R₂₀ eachtogether mean —CH═CR₂₄—CR₂₅═CH—, —N═CR₂₄—CR₂₅═CH—, —CH═CR₂₄—CR₂₅═N—,—CH═N—CR₂₅═CH—, —CH═CR₂₄—N═CH—.

[0239] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ and R₂₀ is alkyl, it maybe linear alkylor branched alkyl, and contain preferably 1 to 12 and more preferably 1to 6 carbon atoms. Examples for alkyl have been given before. Preferredalkyls are methyl, ethyl, n- or i-propyl, n-, I- and t-butyl, and theisomers of pentyl and hexyl.

[0240] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ and R₂₀ is alkoxy, it maybe linearalkoxy or branched alkoxy, and contain preferably 1 to 12 and morepreferably 1 to 6 carbon atoms. Examples for alkoxy have been givenbefore. Preferred alkoxies are methoxy, ethoxy, n- or i-propoxy, n-, I-and t-buoxty, and the isomers of pentoxy and hexoxy.

[0241] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ and R₂₀ is alkylthiols, it maybe linearalkylthiol or branched alkylthiol, and contain preferably 1 to 12 andmore preferably 1 to 6 carbon atoms. Examples for alkylthio have beengiven before. Preferred alkylthiols are methylthio, ethylthio, n- ori-propylthio, n-, I- and t-butylthio, and the isomers of pentylthio andhexylthio.

[0242] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ and R₂₀ is C₁ to C₁₂alkoxy-polyC₂ toC₆oxyalkylene, the alkoxy maybe linear alkoxy or branched alkoxy andcontains preferably 1 to 6 and more preferably 1 to 4 carbon atoms andmay be for example methoxy, ethoxy, propoxy and butoxy. The oxyalkylenegroup preferably contains 2 to 4 and more preferably 2 or 3 carbon atomsand may be ethylenoxy or 1,2-propylenoxy. The residue may contain 1 to12, preferably 1 to 6, and more preferably 1 to 4 repeating oxyalkyleneunits.

[0243] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅is and R₁₆ as well as R₁₇, R₁₈, R₁₉ and R₂₀ is cycloalkyl, it ispreferably cyclopentyl or cyclohexyl.

[0244] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ and R₂₀ is cycloalkoxy it is preferablycyclopentoxy or cyclohexoxy.

[0245] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ and R₂₀ is cycloalkyltho it ispreferably cyclopentylthio or cyclohexylthio.

[0246] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ and R₂₀ is cycloalkyl-alkyl, the alkylis preferably ethyl and most preferably methyl, and the cycloalkyl ispreferably cyclopentyl or cyclohexyl. Preferred examples arecyclopentylmethyl and cyclohexylmethyl.

[0247] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ and is cycloalkyl-alkoxy, the alkoxy ispreferably ethoxy and most preferably methoxy, and the cycloalkyl ispreferably cyclopentyl or cyclohexyl. Preferred examples arecyclopentyl-methoxy and cyclohexylmethoxy.

[0248] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ is cycloalkyl-alkylthio, the alkylthiois preferably ethylthio and most preferably methylthio, and thecycloalkyl is preferably cyclopentyl or cyclohexyl. Preferred examplesare cyclopentyl-methylthio and cyclohexylmethylthio.

[0249] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ and R₂₀ is phenylalkyl the alkyl grouppreferably contains 1 or 2 carbon atoms and mostly preferred is methyl.Especially preferred is benzyl.

[0250] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ and R₂₀ is phenylalkoxy, the alkoxygroup preferably contains 1 or 2 carbon atoms and mostly preferred ismethoxy. Especially preferred is benzyloxy.

[0251] In the context of the invention when one or more of R₁₃, R₁₄, R₁₅and R₁₆ as well as R₁₇, R₁₈, R₁₉ and R₂₀ is phenylalkylthio, thealkylthio group preferably contains 1 or 2 carbon atoms and mostlypreferred is methylthio. Especially preferred is benzylthio.

[0252] In the context of the invention when one or more of R₁₇, R₁₈, R₁₉and R₂₀ is phenyl-C₂ to C₁₂alkylidene, the alkylidene may be linear orbranched and may contain 2 to 6 and preferably 2 to 4 carbon atoms. Someexamples are ethylidene, 1,1- or 2,2-propylidene, and 1,1- or2,2-butylidene.

[0253] Preferred substituents are F, Cl, C₁ to C₄alkyl, C₁ to C₄alkoxy,C₁ to C₄alkylthio, and —NR₂₁R₂₂, wherein R₂₁ and R₂₂ are independentlyfrom one another is C₁ to C₁₂alkyl, phenyl or benzyl.

[0254] In the context of the invention when R₂₁ and R₂₂ are alkyl it maybe linear alkyl or branched alkyl and may contain 1 to 12 and preferably1 to 6 carbon atoms.

[0255] In the context of the invention when R₂₁ and R₂₂ are alkylphenyl,the alkyl may be linear or branched and may contain 1 to 8 andpreferably 1 to 6 carbon atoms.

[0256] In the context of the invention when R₂₁ and R₂₂ are alkylbenzyl,the alkyl may be linear or branched and may contain 1 to 8 andpreferably 1 to 6 carbon atoms.

[0257] R₂₃ is preferably H, methyl or ethyl.

[0258] In the context of the invention when R₂₄ and R₂₅ are alkyl,alkoxy, alkylthio may be linear or branched and may contain 1 to 4 andpreferably 1 or 2 carbon atoms.

[0259] In a preferred embodiment R₁₃, R₁₄, R₁₅ and R₁₆ are preferably C₁to C₄alkyl, C₁ to C₄alkoxy, phenyl, or C₁ to C₄alkylphenyl. Mostlypreferred R₁₃, R₁₄, R₁₅ and R₁₆ are all phenyl.

[0260] In still a further preferred embodiment R₁₇ and R₂₀ are H, andR₁₈ and R₁₉ or both are C₁ to C₁₈alkyl or C₁ to C₁₈alkoxy, or R₁₇ andR₁₈, R₁₉ and R₂₀, R₁₈ and R₁₉, or R₁₇ and R₁₈ and R₁₉ and R₂₀ eachtogether mean —CH═CR₂₄—CR₂₅═CH—, wherein R₂₄ and R₂₅ mean independentlyfrom one another H, F, Cl, C₁ to C₈alkyl or C₁ to C₈alkoxy.

[0261] In an especially preferred embodiment the compounds of formula Vcorrespond to formula VI,

[0262] wherein

[0263] R₁₇ and R₂₀ are H, and R₁₈ and R₁₉ or both are C₁ to C₁₈alkyl orC₁ to C₁₈alkoxy, or R₁₈ and R₁₉ together mean —CH═CR₂₄—CR₂₅═CH—; or R₁₇and R₁₈ together or R₁₉ and R₂₀ together, or R₁₇ and R₁₈ together andR₁₉ and R₂₀ together mean —CH═CR₂₄—CR₂₅═CH—, wherein R₂₄ and R₂₅ areindependently from one another H, F, Cl, C₁ to C₈alkyl or C₁ toC₈alkoxy. The alkyl is preferably branched in the α- or α,α-position.

[0264] It was also found that 1,2,3,4-tetrachloro-benzo [4,5] imidazo[2,1-a] isoindol-11-ones with α-branched alkyl substituents possess ahigher light stability than the methyl substituted compounds, and thatacyl substituted 1,2,3,4-tetrachloro-benzo [4,35] imidazo [2,1-a]isoindol-11-ones have also a high light stability and a desiredsolubility. A further embodiment of the invention are compounds of theformula VIa,

[0265] wherein

[0266] X₁ is Cl or Br,

[0267] one of R′₁₈ and R′₁₉ or both are independently from one another—COOH, or α- or α,α-branched C₃ to C₂₀alkyl or R_(a)—C(O)—, whereinR_(a) means C₁ to C₂₀alkyl; or C₅ to C₈cycloalkyl, C₅ toC₈cycloalkyl-CH₂—, phenyl, benzyl, which are unsubstituted orsubstituted with halogen, C₁ to C₁₂alkyl or C₁ to C₁₂alkoxy, or

[0268] one of R′₁₈ and R′₁₉ is α- or α,α-branched C₃ to C₂₀alkyl orR_(a)—C(O)—, wherein R_(a) means C₁ to C₂₀alkyl; or C₅ to C₈cycloalkyl,C₅ to C₈cycloalkyl-CH₂—, phenyl, benzyl, which are unsubstituted orsubstituted with halogen, C₁ to C₁₂alkyl or C₁ to C₁₂alkoxy, and theother of R′₁₈ and R′₁₉ is linear C₁ to C₁₂alkyl.

[0269] The branched alkyl is preferably selected from 1-methyl or1,1-dimethyl substituted alk-1-yl. The alkyl preferably contains 3 to18, more preferably 3 to 12, and most preferably 3 to 8 carbon atoms. X₁is preferably Cl.

[0270] R_(a) means preferably C₃ to C₁₂alkyl; or cyclopentyl,cyclohexyl, phenyl, benzyl, which are unsubstituted or substituted withF, Cl, Br, C₁ to C₆alkyl or C₁ to C₆alkoxy.

[0271] In the context of the invention the linear alkyl containspreferably 1 to 8, more preferably 1 to 6, and most preferably 1 to 4carbon atoms.

[0272] Compounds of the formulae V, VI and Via can be prepared inanalogy to known methods, e.g. described in EP-A 456 609, wherein thepreparation method is based on the following equation:

[0273] Usually the two isomers indicated above are obtained which can beseparated, if desired, e.g. by column chromatography. In general, it isnot necessary for the success of this invention to separate the twostructural isomers.

[0274] Another preferred embodiment of the present invention relates tothe use of the inventive compounds V, VI and VIa as organic emittingmaterials in and for the preparation of electroluminescence (“EL”)devices. Those EL-devices are well known in the art and e.g. describedin U.S. Pat. No. 5,593,788, WO 94/15441, and the literature citedtherein. For example one of the common EL devices comprises twoextremely thin layers (<1.0 μm in combined thickness) which separate theanode and the cathode. One layer specifically is chosen to inject andtransport holes and the other specifically chosen to inject andtransport electrons and also acting as the organic luminescent zone ofthe device. The extremely thin organic luminescent medium offers reducedresistance, permitting higher current densities for a given level ofelectrical biasing. Since light emission is directly related to currentdensity through the organic luminescent medium, the thin layers coupledwith increased charge injection and transport efficiencies have allowedacceptable light emission levels (e.g. brightness levels capable ofbeing visually detected in ambient light) to be achieved with lowvoltages in ranges compatible with integrated circuit drivers, such astransporting layer also acting as the luminescent zone of the device.

[0275] In another preferred embodiment of this invention, the inventivehost/guest compositions can be used as organic emitting material in alayer of an EL device as well as for the preparation of such an ELdevice. Such devices are known in principle e.g. from U.S. Pat. No.5,593,788 and the prior art cited therein, hence, no further details arenecessary for a skilled person in the art.

[0276] Hence, electroluminescent devices comprising the inventivecompounds or compositions are also part of this invention. Thepreparation of such devices is given in detail e.g. in the above citedU.S. Pat. No. 5,593,788 or WO 94/15441.

[0277] The fluorescent composition of the present invention emits solidstate fluorescence with a greatly enhanced emission intensity whencompared to the solid-state emission intensity of a powder that containshost units but lacks any guest units, or a powder that contains guestunits but lacks any host units.

[0278] The compositions on hand do show the following advantagescompared to known compositions:

[0279] a) a greatly enhanced and intense fluorescence emission isgenerated,

[0280] b) an intense solid state fluorescence is imparted, wherein theemission wavelengths are in the in the visible region of theelectromagnetic spectrum,

[0281] c) the composition can be excited using wavelengths in both theUV and visible regions,

[0282] d) very good photostabilities and outdoor durabilities can beachieved,

[0283] e) a wide range of emission wavelengths can be achieved throughselection of guest mole cules (color tuning),

[0284] f) a high thermal stability can be achieved,

[0285] g) easy preparation for the materials i.e. co-precipitation ofthe dissolved components is possible.

[0286] The following examples demonstrate the invention.

[0287] The designation of the benzo [4,5] imidazo [2,1-a]isoindol-11-ones relies on the following formula:

A) Preparation of benzo [4,5] imidazo [2,1-a] isoindol-11-ones EXAMPLEA1 1,2,3,4-tetraphenylbenzo [4,5] imidazo [2,1-a] isoindol-11-one-7(or8, A′1)-carboxylic acid (A1)

[0288] A 300 ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 4.58 g (30.1 mmol) of 3,4-diaminobenzoic acid,13.6 g (30.0 mmol) of 1,2,3,4-tetraphenylphthalic anhydride, and 100 mlof glacial acetic acid. Under nitrogen atmosphere, the mixture isstirred and heated at reflux for 5 hours. The slurry is cooled and theyellow solid is isolated by filtration. The solid is washed with waterand then with methanol. 10.9 g of yellow solid is obtained (64%).

[0289] 1H-NMR (CDCl₃, TMS): δ8.43 (d, J=1.2 Hz, 1H, H_(A9) or H_(A′6)),8.33 (d, J=0.9 Hz, 1H, H_(A9) or H_(A′6)), 8.05 (dd, J=1.5, 8.4 Hz, 1H,H_(A7) or H_(A′8)), 7.96 (dd, J=1.6, 8.5 Hz, 1H, H_(A7) or H_(A′8)),7.72 (d, J=8.3 Hz, 1H, H_(A6) or H_(A′9)), 7.61 (d, J=8.5 Hz, 1H, H_(A6)or H_(A′9)), 7.30-7.24 (m, 8H), 7.18-7.15 (m, 2H), 6.92-6.89 (m, 6H)6.81-6.76 (m, 4H).

EXAMPLE A2 1,2,3,4-tetraphenyl-7-(t-butyl)-benzo [4,5] imidazo [2,1-a]isoindol-11-one (A2) and 1,2,3,4-tetraphenyl-8-(t-butyl)-benzo [4,5]imidazo [2,1-a] isoindol-11-one (A′2)

[0290] A 100 ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 0.99 g (6.01 mmol) of4-(t-butyl)-o-phenylenediamine, 2.73 g (6.03 mmol) of1,2,3,4-tetraphenylphthalic anhydride, and 15 ml of glacial acetic acid.Under nitrogen atmosphere, the mixture is stirred and heated at refluxfor 3 hours. The slurry is cooled and the yellow solid is isolated byfiltration. The solid is washed with water. 2.5 g of yellow solid isobtained (total 71%; 42% for A2 and 29% for A′2). Two isomers can beseparated by column chromatography using CH₂Cl₂ as eluent.

[0291] A2 (7-position):

[0292]¹H-NMR (CDCl₃, TMS): δ7.60 (d, J=1.3 Hz, 1H, H₆), 7.58 (d, J=8.4Hz, 1H, H₉), 7.30 (dd, J=8.5, 1.4 Hz, 1H, H₈), 7.30-7.16 (m, 10H),6.87-6.83 (m, 6H), 6.81-6.76 (m, 4H), 1.29 (s, 9H).

[0293]¹³C-NMR(in CDCl₃): δ160.3 (s, C=0), 156.1 (s, C_(4b)), 149.6 (dt,C_(5a)), 148.3 (m, C₇), 147.9 (t, C₃), 145.5 (t, C₂), 141.9 (t, C₄ orC₁), 138.4 (m), 138.1 (m), 137.7 (C₄ or C₁), 136.1 (m), 135.5 (m),130.9, 130.8, 130.3, 130.1 (s), 129.8, 127.7, 127.5, 127.1, 127.0,126.4, 126.3, 123.9 (dm, J¹=160 Hz, C₈), 118.7 (dd, J₁=160 Hz, C₆),111.6 (d, J¹=170 Hz, C₉), 35.0 (CMe₃), 31.6 (CH₃).

[0294] A′2 (8-position):

[0295]¹H-NMR (CDCl₃, TMS): δ7.73 (d, J=1.6 Hz, 1H, H₉), 7.47 (d, J=8.6Hz, 1H, H₆), 7.28-7.22 (m, 9H), 7.20-7.17 (m, 2H), 6.93-6.89 (m, 6H),6.82-6.78 (m, 4H), 1.32 (s, 9H). ¹³C-NMR (CDCl₃): δ160.6 (s, C=0), 155.6(s, C₂), 150.3 (m, C₈), 147.9 (t, C₃), 147.4 (ddd, C_(5a)), 145.4 (t,C₂), 141.9 (t), 138.4 (m), 138.0 (m), 137.6 (t), 136.0 (m), 135.6 (m),130.9, 130.8, 130.4, 130.2 (s), 129.8, 127.7, 127.5, 127.4, 127.1,127.0, 126.3, 126.2, 122.4 (dd, J¹=160 Hz, C₇), 121.1 (d, J¹=160 Hz,C₆), 109.3 (ddd, J¹=160 Hz, C₉), 35.2 (CMe₃), 31.5 (CH₃).

EXAMPLE A3 1,2,3,4-tetraphenylbenzo [4,5] imidazo [2,1-a]isoindol-11-one (A3)

[0296] A 500 ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 8.34 9 (73.3 mmol) of o-phenylenediamine(95%), 33.0 g (66.3 mmol) of 1,2,3,4-tetraphenylphthalic anhydride, and200 ml of glacial acetic acid. Under nitrogen atmosphere, the mixture isstirred and heated at reflux for 11 hours. The slurry is cooled and theyellow solid is isolated by filtration. The solid is washed with waterand then with methanol. 35.1 g of an yellow solid is obtained (92%).

[0297]¹H-NMR (CDCl₃, TMS): δ7.66 (d, J=7.6 Hz, 1H), 7.55 (d, J=7.7 Hz,1H), 7.30-7.15 (m, 12H), 6.93-6.88 (m, 6H), 6.81-6.76 (m, 4H). MS: 524([M]⁺).

EXAMPLE A4 1,2,3,4-tetraphenyl-7(or 8)-nitro-benzo [4,5] imidazo [2,1-a]isoindol-11-one (A4, A′4)

[0298] A 100 ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 1.53 g (9.99 mmol) of4-nitro-o-phenylenediamine, 4.53 g (10.0 mmol) of1,2,3,4-tetraphenylphthalic anhydride, and 25 ml of glacial acetic acid.Under nitrogen atmosphere, the mixture is stirred and heated at refluxfor 1.33 hours. The slurry is cooled and the yellow solid is isolated byfiltration. The solid is washed with water and then with methanol. 6.1 gof a pale yellow solid is obtained (100%).

[0299]¹H-NMR (CDCl₃, TMS): δ8.57 (d, J=2.2 Hz, 1H, H_(A9) or H_(A′6)),8.48 (d, J=2.1 Hz, 1H, H_(A9) or H_(A′6)), 8.22 (dd, J=2.1, 8.8 Hz, 1H,H_(A7) or H_(A′8)), 8.13 (dd, 1H, H_(A7) or H_(A′8)), 7.75 (d, J=8.8 Hz,1H, H_(A6) or H_(A′9)), 7.65 (d, J=8.9 Hz, 1H, H_(A6) or H_(A′9)),7.32-7.23 (m, 8H), 7.18-7.15 (m, 2H), 6.95-6.90 (m, 6H), 6.81-6.76 (m,4H).

[0300] MS: 569 ([M]⁺).

EXAMPLE A5 1,2,3,4-tetraphenyl-7(or 8)-methyl-benzo [4,5] imidazo[2,1-a] isoindol-11-one (A5, A′5)

[0301] A 100ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 1.30 g (10.64 mmol) of4-methyl-o-phenylenediamine, 4.53 g (10.01 mmol) of1,2,3,4-tetraphenylphthalic anhydride, and 25 ml of glacial acetic acid.Under nitrogen atmosphere, the mixture is stirred and heated at refluxfor 5 hours. The slurry is cooled and the yellow solid is isolated byfiltration. The solid is washed with water and MeOH. 4.16 g of a yellowsolid is obtained (77%).

[0302]¹H-NMR (CDCl₃, TMS): δ7.52 (d, J=8.1 Hz, 1H, H_(A6) or H_(A′9)),7.48 (br s, 1H, H_(A9) or H_(A′6)), 7.42 (d, J=8.2 Hz, 1H, H_(A6) orH_(A′9)), 7.36 (br s, 1H, H_(A9) or H_(A′6)), 7.27-7.23 (m, 8H),7.18-7.15 (m, 2H), 7.06 (br d, 1H, H_(A7) or H_(A′8)), 6.99 (br d, 1H,H_(A7) or H_(A′8)), 6.92-6.88 (m, 6H), 6.80-6.75 (m, 4H).

[0303] MS: 538 ([M]⁺), 537 ([M−H]⁺).

EXAMPLE A6 1,2,3,4-tetraphenyl-7(or 8)-methoxy-benzo [4,5] imidazo[2,1-a] isoindol-11-one (A6, A′5).

[0304] A 100 ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 1.38 g (9.99 mmol) of4-methoxy-o-phenylenediamine, 4.52 g (9.99 mmol) of1,2,3,4-tetraphenylphthalic anhydride, and 20 ml of glacial acetic acid.Under nitrogen atmosphere, the mixture is stirred and heated at refluxfor 7 hours. The slurry is cooled and the yellow solid is isolated byfiltration. The solid is washed with water, followed by purificationwith column chromatography. 3.75 g of yellow solid is obtained (68%).

[0305]¹H-NMR (CDCl₃, TMS): δ7.52 (d, J=8.6 Hz, 1H, H_(A6) or H_(A′9)),7.42 (d, J=8.9 Hz, 1H, H_(A6) or H_(A′9)), 7.27-7.23 (m, 8H), 7.20 (d,J=2.6 Hz, 1H, H_(A9) or H_(A′6)), 7.19-7.14 (m, 2H), 7.08 (d, J=2.4 Hz,1H, H_(A9) or H_(A′6)), 6.92-6.88 (m, 6H), 6.85 (dd, 1H, J=2.4, 8.7 Hz,H_(A7) or H_(A′8)), 6.80-6.74 (m, 1H, H_(A7) or H_(A′8)+4H).

[0306] MS: 554 ([M]⁺).

EXAMPLE A7 1,2,3,4-tetraphenyl-6,7-8,9-dibenzo-benzo [4,5] imidazo[2,1-a] isoindol-11-one (A7)

[0307] A 100ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 0.84 g (4.03 mmol) of9,10-diaminophenanthrene, 1.83 g (4.04 mmol) of1,2,3,4-tetraphenylphthalic anhydride, and 15 ml of glacial acetic acid.Under nitrogen atmosphere, the mixture is stirred and heated at refluxfor 5 hours. The slurry is cooled and the orange solid is isolated byfiltration. The solid is washed with water and MeOH, followed bypurification with column chromatography. 2.01 g of an orange solid isobtained (80%).

[0308]¹H-NMR (CDCl₃, TMS): δ9.19 (dd, J=1.5, 8.0 Hz, 1H, H₉ or H₁₀),8.70 (dd, J=7.8 Hz, 1H, H₉ or H₁₀), 8.64 (m, 1H, H₆ or H₁₃), 8.32 (m,1H, H₆ or H₁₃), 7.64-7.59 (m, 4H, H_(7,8,11,12)), 7.37-7.28 (m, 8H),7.25-7.22 (m, 2H), 6.96-6.90 (m, 6H), 6.86-6.79 (m, 4H).

EXAMPLE A8 1,2,3,4-tetrachloro-7(or 8)-nitro-benzo [4,5] imidazo [2,1-a]isoindol-11-one (A8, A′8)

[0309] A 200ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 2.30 g (15.0 mmol) of4-nitro-o-phenylenediamine, 4.29 g (15.0 mmol) of1,2,3,4-tetrachlorophthalic anhydride, and 60 ml of glacial acetic acid.Under nitrogen atmosphere, the mixture is stirred and heated at refluxfor 2 hours. The slurry is cooled and the pale yellow solid is isolatedby filtration. The solid is washed with water and MeOH. 5.48 g of a paleyellow solid is obtained (91%).

[0310]¹H-NMR (CDCl₃, TMS): δ8.75 (dd, J=1.7 Hz, 1H, H_(A9) or H_(A′6)),8.74 (dd, J=2.3Hz, 1H, H_(A9) or H_(A′6)), 8.40 (dd, J=2.2, 8.8 Hz, 1H,H_(A7) or H_(A′8)), 8.32 (dd, J=2.3, 8.9 Hz, 1H, H_(A7) or H_(A′8)),7.97 (dd, J=8.7 Hz, 1H, H_(A6) or H_(A′9)), 7.96 (dd, J=9.0 Hz, 1H,H_(A6) or H_(A′9)).

[0311] MS: 403 ([M+2]⁺), 401 ([M]⁺).

EXAMPLE A9 1,2,3,4-tetrachlorobenzo [4,5] imidazo [2,1-a]isoindol-11-one-7(or 8)-carboxylic Acid (A9, A′9)

[0312] A 1 l round-bottom flask equipped with a stirrer and refluxcondenser is charged with 15.2 g (100 mmol) of 3,4-diaminobenzoic acid,28.6 g (100 mmol) of tetrachlorophthalic anhydride, and 450 ml ofglacial acetic acid. Under nitrogen atmosphere, the mixture is stirredand heated at reflux for 15 hours. The slurry is cooled and the greenishyellow solid is isolated by filtration. The solid is washed with waterand methanol. 37.0 g of a greenish yellow solid is obtained (92%).

[0313] MS: 404 ([M+4]+), 402 ([M+2]+), 400 ([M]+), 387 ([M+4-OH]+), 385([M+2-OH]+), 383 ([M-OH]+).

EXAMPLE A10 1,2,3,4-tetrachloro-7(or 8)-(t-butyl)-benzo [4,5] imidazo[2,1-a] isoindol-11-one (A10, A′10)

[0314] A 100 ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 2.48 g (15.1 mmol) of4-(2′-methyl-2′-propyl)-o-phenylenediamine, 4.30 g (15.0 mmol) oftetrachlorophthalic anhydride, and 40 ml of glacial acetic acid. Undernitrogen atmosphere, the mixture is stirred and heated at reflux for 3.5hours. The slurry is cooled and the yellow solid is isolated byfiltration. The solid is washed with water and methanol. 5.22 g of ayellow solid is obtained (84%).

[0315]¹H-NMR (CDCl₃, TMS): δ7.82 (dd, J=0.5, 1.8 Hz, 1H, H_(A9) orH_(A′6)), 7.73 (dd, J=0.5, 8.6 Hz, 1H, H_(A6) or H_(A′9)), 7.42 (dd,J=1.8, 8.6 Hz, 1H, H_(A7) or H_(A′8)), 1.40 (s, 9H).

[0316] MS: 416 ([M+4]+), 414 ([M+2]+), 412 ([M]+), 401 ([M+4-CH3]+), 399([M+2-CH3]+), 397 ([M-cu3]+).

EXAMPLE A11 1,2,3,4-tetrachloro-7(or 8)-benzoyl-benzo [4,5] imidazo[2,1-a] isoindol-11-one (A11, A′11)

[0317] A 100ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 2.13 g (10.0 mmol) of 3,4-diaminobenzophenone,2.87 g (10.0 mmol) of tetrachlorophthalic anhydride, and 23 ml ofglacial acetic acid. Under nitrogen atmosphere, the mixture is stirredand heated at reflux for 3.5 hours. The slurry is cooled and the yellowsolid is isolated by filtration. The solid is washed with water andmethanol, followed by dissolving in hot CHCl₃ with a soxhlet extractorto remove insoluble impurities. After condensation, 3.36 g of a yellowsolid is obtained (72%).

[0318]¹H-NMR (CDCl₃, TMS): δ8.28 (dd, 1H, H_(A9) or H_(A′6)), 7.93 (dd,J=0.7, 8.5 Hz, 1H, H_(A6) or H_(A′9)), 7.87-7.82 (m, 3H, H_(A7) orH_(A′8), and H2′, 6′), 7.64 (tt. J=1.2, 7.5 Hz, 1H, H_(3′,5′)) 7.52 (t,J=7.6 Hz. 2H, H_(4′)).

[0319] MS: 464 ([M+4]⁺), 462 ([M+2]⁺), 460 ([M]⁺), 387 ([M+4-C₆H₅]⁺),385 ([M+2-C₆H₅]⁺), 383 ([M-C₆H₅]⁺), 359 ([M+4-C₆H₅CO]⁺), 357([M+2-C₆H₅CO]⁺), 355 ([M-C₆H₅CO]⁺).

EXAMPLE A12 1,2,3,4-tetrachloro-benzo [4,5] imidazo [2,1-a]isoindol-11-one (A12)

[0320] Compound A12 is prepared according to the procedure described inEP-A-0 456 609.

[0321] B) Preparation of Guest Chromophores

EXAMPLE B1 N,N′-dibenzyl-quinacridone (B1)

[0322] A 500 ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 3.13 g (10.0 mmol) of quinacridone(hereinafter referred to QA), 17.11 g (100 mmol) of benzyl bromide,138.21 g (1.00 mol) of K₂CO₃ and 200 ml of dimethylformamide (DMF).Under a nitrogen atmosphere, the mixture is stirred and heated at refluxfor 7.5 hours. The slurry is cooled and the orange solid is isolated byfiltration. The solid is washed with water acetone and ethanol. Thereyields 4.34 g of an orange solid (88%).

[0323]¹H-NMR (DMSO-d₆, Dimethylsulfoxide(DMSO)): δ8.56 (s, 2H, H₁), 8.35(dd, J=7.9 Hz, 2H, H₅), 7.79 (dt, J=8.2 Hz, 2H, H₄), 7.67(d, J=8.6 Hz,2H, H₂), 7.37 (t, 4H, H₃), 7.33 (t, 2H, H₆), 7.31 (t, 2H, H₇), 7.27 (d,4H, H₈), 5.29 (s, 4H, H₉).

EXAMPLE B2 N,N′-dibenzyl-diphenyl-diketopyrrolopyrrol

[0324] A 100ml round-bottom flask equipped with a stirrer and refluxcondenser is charged with 1.47 g (5.1 mmol) ofdiphenyl-diketopyrrolopyrrole (hereinafter referred to DPP), 3.44 g(20.1 mmol) of benzyl bromide, 1.38 g (10.0 mmol) of K₂CO₃ and 50 ml ofDMF. Under nitrogen atmosphere, the mixture is stirred and heated at100° C. for 42.5 hours. The slurry is cooled and the orange solid isisolated by filtration. The solid is washed with water and MeOH,followed by dissolving in hot CHCl₃. This CHCl₃ solution is applied tosilica gel column using CH₂Cl₂ as eluent. After condensation, 1.21 g ofan orange solid is obtained (51%).

[0325]¹H-NMR (CDCl₃, TMS): δ7.75 (d, J=7.1 Hz, 4H, H₁), 7.49-7.43 (m,6H, H₂ and H₃), 7.30 (t, J=7.4 Hz 4H H₅) 7.24 (t, J=7.3 Hz, 2H, H₆),7.19 (d, J=7.4 Hz, 4H, H₄), 4.99 (s, 4H, H₇).

[0326] MS: 468 ([M]+).

[0327] C) Preparation of Fluorescent Compositions

EXAMPLE C1

[0328] 1.0×10⁻⁴ mol (0.0557 g) of A1 as a host compound and variousamounts of Rhodamine 19 (Kodak Laboratory Chemicals) as a guest compound(B3) or Rhodamine 6G (Kodak Laboratory Chemicals) as a guest compound(B4) are dissolved in 20 ml of 1,2-dichloroethane and mixed. The solventis then evaporated using a rotary evaporator (RE47, Yamato ScientificCo., LTD.) to obtain fluorescent powders including A1 and B3 or B4 ofvarious concentrations.

[0329] Photoluminescence spectra of the fluorescent powders are measuredusing a fluorescence spectrophotometer in standard reflection mode(F-4500, HITACHI Co., LTD.) with a solid sample holder by exciting thehost compound at absorption band thereof with monochromic light(λ_(max)=360 nm). The results are listed in Table 1. TABLE 1 Fluorescentproperties of fluorescent powders Guest concentration Photoluminescencespectrum Host Guest (mol %) Peak wavelength (nm) Peak intensity A1 none0 512 545 A1 B3 0.1 571 987 A1 B3 0.2 573 1040 A1 B3 0.5 580 869 A1 B40.2 579 968

EXAMPLE C2

[0330] 1.0×10⁻⁴ mol (0.0557 g) of A1 and various amounts of B1 aredissolved in 20 ml of 1,2-dichloroethane and mixed. The solvent is thensublimed by freeze-drying with a freeze-dryer (FD81. Tokyo RikakikaiCo., LTD.) to obtain fluorescent powders including A1 and B1 of variousconcentrations. Photoluminescence spectra of the fluorescent powders aremeasured in the same manner as in Example C1. The results are listed inTable 2. TABLE 2 Fluorescent properties of fluorescent powders includingA1 and B1 Guest concentration Photoluminescence spectrum Host Guest (mol%) Peak wavelength (nm) Peak intensity A1 none 0 510 570 A1 B1 0.1 563687 A1 B1 0.2 565 1014 A1 B1 0.5 564 964

EXAMPLE C3

[0331] 3.0×10⁻⁴ mol (0.1706 g) of A2 or A′2 as a host compound andvarious amounts of B1 or B2 as a guest compound are dissolved in 20 mlof 1-methyl-2-pyrrolidone and mixed. The solution is then poured into400 ml of water which is vigorously stirred with a homogenizer(ULTRA-TURRAX T25. IKA-Labortechnik). A precipitate is filtered anddried in vacuo at 60° C. to obtain fluorescent powders including A2 orA3 and B1 or B2 of various concentrations. Photoluminescence spectra ofthe fluorescent powders are measured in the same manner as in ExampleC1. The results are listed in Tables 3 and 4. TABLE 3 Fluorescentproperties of fluorescent powders including A2 and B1 or B2 Guestconcentration Photoluminescence spectrum Host Guest (mol %) Peakwavelength (nm) Peak intensity A2 none 0 526 197 A2 B1 0.2 523 1155 A2B1 0.5 524 2005 A2 B1 1.0 526 2555 A2 B1 2.0 528 2876 A2 B1 5.0 529 1579A2 B2 1.0 534 2054 A2 B2 2.0 537 2324 A2 B2 5.0 542 2160

[0332] TABLE 4 Fluorescent properties of fluorescent powders includingA′2 and B1 of Guest concentration Photoluminescence spectrum Host Guest(mol %) Peak wavelength (nm) Peak intensity A′2 none 0 522 552 A′2 B11.0 524 2854 A′2 B1 2.0 525 3942 A′2 B1 5.0 529 2227

EXAMPLE C4

[0333] Carefully measured amounts of A1 as a host compound, B1 as aguest compound and an acrylic polymer (PMMA; polymethylmethacrylate,Aldrich Chemical Co. Inc.) are dissolved in CHCl_(3/)methanol (95/5 vol.%) (Wako Chemical Co. Ltd.), to yield a clear, homogeneous solution (5wt% concentration). The mixture is then cast onto a glass substrate usinga wire bar (KCC rod No. 8, RK Print-Coat Instruments) and the solventremoved. At this point the polymer film has the visual color andspectroscopic features typical of the precursor. Photoluminescencespectra of the fluorescent films are measured in the same manner as inExample C1. The results are listed in Table 5. TABLE 5 Fluorescentproperties of the polymer films A1 B1 PMMA Photoluminescence spectrum(wt %) (wt %) (wt %) Peak wavelength (nm) Peak intensity 5 0 95 501 4015 0.05 95 545 561 5 0.1 95 548 564 5 0.2 95 552 586 5 0.3 95 555 788 100 90 501 440 10 0.05 90 546 593 10 0.1 90 551 819 10 0.2 90 553 811 100.3 90 559 896 30 0 70 501 461 30 0.05 70 551 621 30 0.1 70 552 781 300.2 70 556 734 30 0.3 70 558 799

EXAMPLE C5

[0334] 0.1 g of the fluorescent powder of Example C3, which includes A2as host and B2 as guest, is dispersed in 1.0 g of a functional acrylatemonomer [KAYARAD D310 (Nippon Kayaku Co.)] using a homogenizer(ULTRA-TURRAX T25. IKA-Labortechnik). 5.0 g of a 10 wt % ofpolyvinyalcohol (PVA-117, Kurare) aqueous solution is added over theperiod of about 10 minutes to the vigorously stirred dispersion to givean uniform suspension, and recrystallized K₂S₂O₈ as initiator is addedat room temperature. The reaction mixture is removed of oxygen bybubbling with N₂ gas for approximately 30 minutes, then placed in atemperature controlled water bath at 80° C. for 10 hours. Highlycross-linked polymer particles containing fluorescent powder areobtained and isolated by filtration. The particles are then washedoftentimes with water and methanol. Drying is performed in a vacuum ovenat 60° C. overnight. Yield 34.4%. Photoluminescence spectra of thefluorescent polymer particles are measured in the same manner asdescribed in Example C1. The results are listed in Table 6. TABLE 6Fluorescent properties of fluorescent polymer powders. Guestconcentration Photoluminescence spectrum Host Guest (mol %) Peakwavelength (nm) Peak intensity A2 none 0 525 370 A2 B2 5.0 538 1520

EXAMPLE C6

[0335] 0.1 g of A2 as host, none or 0.002 g of B2 as guest and 1.0 g ofa functional acrylate monomer (KAYARAD D310) are dissolved in 10 ml of1-methyl-2-pyrrolidone. The solution is then poured dropwise into 200 mlof 2 wt % of polyvinyalcohol (PVA-117, Kurare) aqueous solution which isvigorously stirred with a homogenizer. A yellow precipitate with greenfluorescence is immediately generated, to which the recrystallizedinitiator K₂S₂O₈ is added. The reaction mixture is removed of oxygen bybubbling through N₂ gas for approximately 30 minutes, and placed in atemperature controlled water bath at 80° C. for 10 hours. Highlycrosslinked polymer particles are obtained and isolated by filtration.The particles are then washed oftentimes with water and methanol. Dryingis performed in a vacuum oven at 60° C. overnight. Yield 42.5%.Photoluminescence spectra of the fluorescent polymer particles aremeasured in the same manner as described in Example C1. The results arelisted in Table 7. TABLE 7 Fluorescent properties of fluorescent polymerpowders. Guest concentration Photoluminescence spectrum Host Guest (mol%) Peak wavelength (nm) Peak intensity A2 none 0 524 410 A2 B2 2.0 5311790

EXAMPLE C7

[0336] To an all glass reaction flask fitted with a rubber seal,magnetic stirrer, and maintained under a nitrogen atmosphere, 30 ml ofdegassed water is charged and heated to 60° C. Maintaining the reactiontemperature of 60° C., a degassed slurry of 2.08 g (20 wt %) A12, 5.12 g(49 wt %) ethylene glycol dimethacrylate, 3.1 g (30 wt %) methylmethacrylate, none or 0.103 g (1 wt %) Lumogen F Orange (BASF), 0.16 g2,2′-Azobis(isobutyronitrile) and 10 ml chloroform are added in a singleaddition. The vigorously stirred reaction is allowed to proceed for 6hours, and then the reaction mixture is filtered. The precipitateconsists of bright orange particles, that are non-uniform in shape andsize. These particles are washed with water several times and dried atthe water aspirator. Final drying is performed in a vacuum oven at 60°C. overnight. Yield 90%. The polymer powder thus obtained is ground intoa fine powder, via a standard laboratory mortar and pestle.Photoluminescence spectra of the fluorescent polymer powders aremeasured in the same manner as described in Example C1. The results arelisted in Table 8. TABLE 8 Fluorescent properties of fluorescent polymerpowders. Guest Photoluminescence spectrum concentration Peak Host Guest(mol %) wavelength (nm) Peak intensity A12 none 0 511 242 A12 Lumogen F1.0 584 680 Orange

EXAMPLE C8 Light Stability of 1,2,3,4-tetraphenylbenzo [4,5] imidazo[2,1-a] isoindol-11-ones

[0337] 1,2,3,4-tetraphenyl-7(or 8)-methoxy-benzo [4,5] imidazo [2,1-a]isoindol-11-one and various derivatives are charged in the sample holderused in Example C1. The samples are exposed to light with a Xenon lampweather-ometer (WEL-15X-HC-B.Ec, Suga Test Instruments Co.) for 100hours under the following conditions: light intensity: 0.35 W/cm² at 340nm, temperature: 63° C. at black panel, humidity: 50%.

[0338] The intensity of the photoluminescence is measured prior to lightexposure and the intensity loss in percent is measured after 100 hoursof light exposure as described in example C1, comparing the peakheights. The results are summarized in table 9. TABLE 9 Light stabilityof stability of 1,2,3,4-tetraphenyl-benzo [4,5] imidazo [2,1-a]isoindol-11-ones. Intensity prior to Intensity after Compound λ_(max)(nm) exposure exposure Loss (%) A3 505 1211 759 37 A2 517 810 751 7 A′2505 2033 1595 22 A5 533 488 390 20 A6 556 45 45 <1 A7 598 159 152 4

EXAMPLE C9 Light Stability of 1,2,3,4-tetrachloro-7-methyl-benzo [4,5]imidazo [2,1-a] isoindol-11-one and Other Derivatives

[0339] The procedure of example C8 is repeated but this time using1,2,3,4-tetrachloro-7-methyl-benzo [4,5] imidazo [2,1-a] isoindol-11-one(A″) as comparison with 1,2,3,4-tetrachloro-7-t-butyl-benzo [4,5]imidazo [2,1-a] isoindol-11-one (A10) and1,2,3,4-tetrachloro-7-benzoyl-benzo [4,5] imidazo [2,1-a]isoindol-11-one (A11). The results are summarized in table 10. TABLE 10Intensity prior to Intensity after Compound λ_(max)(nm) exposureexposure Loss (%) A″ 534 170 142 17 A10 546 156 136 11 A11 524 273 24710

1. A composition comprising (a) an effective amount of a guestchromophore embedded in a matrix of a host chromophore, or (b) a hostchromophore and an effective amount of a guest chromophore both embeddedin a polymer matrix, wherein the absorption spectrum of the guestchromophore overlaps with the fluorescence emission spectrum of the hostchromophore, and wherein the host chromophore is selected from the groupconsisting of benzo [4,5]imidazo [2,1-a]isoindol-11-ones.
 2. Acomposition according to claim 1, characterized in that (a) the guestchromophore is homogeneously distributed within the matrix of the hostchromophore, or (b) the host chromophore and the guest chromophore bothare homogeneously distributed within the polymer matrix.
 3. Acomposition according to claim 1, characterized in that the guestchromophore is selected from the group consisting of quinacridones,perylenes, perinones, diketo- and dithioketopyrrolopyrroles, rhodamines,coumarins, xanthens, oxazines, oxazoles, cyanines, phthalocyanines,porphyrines, styryl dyes, metal complexes and mixtures thereof.
 4. Aprocess for the preparation of a composition according to claim 1,comprising a host chromophore and a guest chromophore and, if desired, apolymer matrix, wherein the absorption spectrum of the guest chromophoreoverlaps with the fluorescence emission spectrum of the hostchromophore, characterized in (a) selecting the host chromophore fromthe group consisting of benzo[4,5]imidazo[2,1-a]-isoindol-11-ones, (b)mixing the host chromophore and an effective amount of at least oneguest chromophore, and optionally a polymer or polymerisable precursor,in the presence of a solvent, and c) then precipitating the host andguest chromophores, optionally in the presence the polymer of step (b),or (d) precipitating the host and guest chromophores duringpolymerization of the polymer precursor of step (b).
 5. A polymerisablecomposition comprising polymerisable monomers or prepolymers inadmixture with a composition of claim 1 in the form of a powdercontaining particles, or with host and guest chromophores according toclaim 1, preferably dissolved therein, or both.
 6. A compositioncomprising a carrier material with a high relief image of a polymerizedphotoresist material, which contains a composition of claim 1 in theform of a powder containing particles, or host and guest chromophoresaccording to claim 1, or both, if desired dissolved and/or homogeneouslydistributed therein.
 7. A process for the preparation of fluorescenthigh relief images on a carrier, characterized in irradiating under amask or by laser writing, the coated photopolymerisable compositionaccording to claim 5, preferably dried and removed of solvent, on thecarrier, developing the irradiated composition and finally removing thenon-irradiated parts.
 8. Method for the use of the compositionsaccording to claim 1 as fluorescent materials.
 9. A compound of theformula V,

wherein at most three of R₁₃, R₁₄, R₁₅ and R₁₆ are H and at least one ofR₁₃, R₁₄, R₁₅ and R₁₆ are a substituent selected from the group of C₁ toC₁₈alkyl, C₁ to C₁₈alkoxy, C₁ to C₁₈alkylthio, C₁ to C₁₂alkoxy-polyC₂ toC₆oxyalkylene; unsubstituted or with F, Cl, Br, —CN, C₁ to C₁₂alkyl, C₁to C₁₂alkoxy, C₁ to C₁₂alkylthio, or-NR₂₁R₂₂ substituted C₅ toCycloalkyl, C₅ to C₈cycloalkoxy, C₅ to C₈cycloalkoxy, C₅ toC8cycloalkylthio, C₅ to C₈cycloalkyl-C₁ to C₄alkyl, C₅ toC₈cycloalkyl-C₁ to C₄alkoxy, C₅ to C₈cycloalkyl-C₁ to C₄alkylthio,phenyl, phenyloxy, phenylthio, phenyl-C₁ to C₄alkyl, phenyl-C₁ toC₄alkoxy, phenyl-C₁ to C₄alkylthio; or R₁₃ and R₁₄ together, R₁₅ and R₁₆together, or R₁₃ and R₁₄ together and R₁₅ and R₁₆ together, or R₁₄ andR₁₅ together are selected from the groups —CH═CR₂₄—CR₂₅═CH—,—N═CR₂₄—CR₂₅═CH—, —CH═CR₂₄—CR₂₅═N—, —CH═N—CR₂₅═CH—, —CH═CR₂₄—N═CH—,—N═CR₂₄—CR₂₅═N—, —N═CR₂₄—N═CH—, —CH═CH—O—, —CH═CH—S—, —CH═CH—NR₂₃—; R₁₇and R₂₀ independently from one another are H or have the meaning of R₁₈;one of R₁₈ and R₁₉ are H and the other of R₁₈ and R₁₉ or both are asubstituent selected from the group of C₁ to C₁₈alkyl, C₁ to C₁₈alkoxy,C₁ to C₁₈alkylthio, C₁ to C₁₂alkoxy-polyC₂ to C₆-oxyalkylene;unsubstituted or with F, Cl, Br, —CN, C₁ to C₁₂alkyl, C₁ to C₁₂alkoxy,C₁ to C₁₂alkylthio, or —NR₂₁R₂₂ substituted C₅ to C₈cycloalkyl, C₅ toC₈cycloalkoxy, C₅ to C₈cycloalkylthio, C₅ to C₈cycloalkyl-C₁ to C₄alkyl,C₅ to C₈cycloalkyl-C₁ to C₄alkoxy, C₅ to C₈cycloalkyl-C₁ to C₄alkylthio,phenyl, phenyloxy, phenylthio, phenyl-C₁ to C₄alkyl, phenyl-C₁ toC₄alkoxy, phenyl-C₁ to C₄alkylthio, phenyl-C₂ to C₁₂alkylidene,phenyl-C(O)—, phenyl-NR₂₃—C(O)—, phenyl-NR₂₃—S(O)₂—, phenyl-S(O)—,phenyl-S(O)₂—, phenyl-CO₂—, phenyl-S(O)—O—, phenyl-SO₃—, phenyl-NR₂₃—,or phenyl-CH═CH—; or R₁₇ and R₁₈ together, R₁₉ and R₂₀ together, or R₁₇and R₁₈ together and R₁₉ and R₂₀ together, or R₁₈ and R₁₉ together areselected from the groups —CH═CR₂₄—CR₂₅═CH—, —N═CR₂₄—CR₂₅═CH—,—CH═CR₂₄—CR₂₅═N—, —CH═N—CR₂₅═CH—, —CH═CR₂₄—N═CH—, —N═CR₂₄—CR₂₅═N—,—N═CR₂₄—N═CH—, —CH═CH—O—, —CH═CH—S—, —CH═CH—NR₂₃—; R₂₁ and R₂₂ areindependently from one another are C₁ to C₂₀alkyl, phenyl, C₁ toC₁₂alkylphenyl, benzyl or C₁ to C₁₂alkylbenzyl, or R₂₁ and R₂₂ togethermean tetramethylene, pentamethylene or —CH₂CH₂—O—CH₂CH₂—; R₂₃ is H C₁ toC₄alkyl or benzyl; and R₂₄ and R₂₅ are independently from one another H,C₁ to C₆alkyl, C₁ to C₆alkoxy, C₁ to C₆alkylthio, or F, Cl or Br.
 10. Acompound according to claim 9, characterized in that it corresponds toformula VI,

wherein R₁₇ and R₂₀ are H, and R₁₈ and R₁₉ or both are C₁ to C₁₈alkyl orC₁ to C₁₈alkoxy, or R₁₈ and R₁₉ together mean —CH═CR₂₄—CR₂₅═CH—; or R₁₇and R₁₈ together or R₁₉ and R₂₀ together R₁₇ and R₁₈ together and R₁₉and R₂₀ together mean —CH═CR₂₄—CR₂₅═CH—, wherein R₂₄ and R₂₅ areindependently from one another H, F, Cl, C₁ to C₈alkyl or C₁ toC₈alkoxy.
 11. A compound of the formula VIa,

wherein X, is Cl or Br, one of R′₁₈ and R′₁₉ or both are independentlyfrom one another —COOH, or α- or α,α-branched C₃ to C₂₀alkyl orR_(a)—C(O)—, wherein R_(a) means C₁ to C₂₀alkyl; or C₅ to C₈cycloalkyl,C₅ to C₈cycloalkyl-CH₂—, phenyl, benzyl, which are unsubstituted orsubstituted with halogen, C₁ to C₁₂alkyl or C₁ to C₁₂alkoxy, or one ofR′₁₈ and R′₁₉ is α- or α,α-branched C₃ to C₂₀alkyl or R_(a)—C(O)—,wherein R_(a) means C₁ to C₂₀alkyl; or C₅ to C₈cycloalkyl, C₅ toC₈cycloalkyl-CH₂—, phenyl, benzyl, which are unsubstituted orsubstituted with halogen, C₁ to C₁₂alkyl or C₁ to C₁₂alkoxy, and theother of R′₁₈ and R′₁₉ is linear C₁ to C₁₂alkyl.
 12. Method for the useof compound V according to claim 9 as organic emitting material in andfor the preparation of electroluminescence (“EL”) devices.
 13. Methodfor the use of compound VI according to claim 10 as organic emittingmaterial in and for the preparation of electroluminescence (“EL”)devices.
 14. Method for the use of compound Vla according to claim 11 asorganic emitting material in and for the preparation ofelectroluminescence (“EL”) devices.
 15. Method for the use of thecompositions according to claim 1 as organic emitting materials in andfor the preparation of electroluminescence (“EL”) devices. 16.Electroluminescence device according to the method of claim
 12. 17.Electroluminescence device according to the method of claim
 13. 18.Electroluminescence device according to the method of claim
 14. 19.Electroluminescence device according to the method of claim 15.